\ 


■Cv~dN 


Columbia  Winihtx^itf  \^^5 
in  tiie  Cit?  of  iSeto  Horfe 

College  of  ^i)?£(ician£;  antj  ^urseonsi 


^titxtntt  %ihvavp 


MICRO-CHEMTSTRY  OF  POISONS, 

INCLUDING    THEIR 

PHYSIOLOGICAL,  PATHOLOGICAL,  AND  LEGAL  RELATIONS; 

WITH 

AN    APPENDIX 

ON    THE 

DETECTION  AND  MICROSCOPIC  DISCRIMINATION  OF  BLOOD: 


ADAPTED    TO 

THE   USE    OF   THE   MEDICAL   JURIST,  PHYSICIAN, 

AND   GENERAL   CHEMIST. 


BY 

THEODORE   G.  WORMLEY,  M.D.,  Ph.D.,  LL.D., 

PROFESSOR   OF   CHEMISTRY   AND   TOXICOLOGT   IN    THE  MEDICAL  DEPARTMENT   OF   THE  rNIVERSITT   OF 

PENNSTLTANIA. 


WITH     NINETY-SIX     ILLUSTRATIONS     UPON     STEEL. 


"Atto  neiprjQ  w&vra  avdpiinoiOL  fcMec  -yivecdai. — Herodotus. 


SECOND    EDITION. 


PHILADELPHIA: 

J.  B.  LIPPINCOTT    COMPANY. 

188  5. 


Copyright,  1886,  by  Theodore  G,  Woemi-ey. 


(SIEREQTYPERS  andPRI  NTE^RSl 


TO 


ifi^t 


WHO, 

BY     HER    SKILFUL    HAND, 
ASSISTED     SO     LARGELY     IN     ITS     PREPARATION, 


%\ih  l^ohm 


^ 


AFFECTIONATELY    INSCRIBED. 


c:K 


Digitized  by  the  Internet  Archive 

in  2010  with  funding  from 

Open  Knowledge  Commons 


http://www.archive.org/details/microchemistryoOOworm 


PREFACE 

TO 

THE    SEOOIS'D   EDITION. 


On  issuing  this  edition  of  the  Micro-Chemistry  of  Poisons, 
nothing  need  be  added  in  regard  to  its  scope  and  design  to  what 
was  said  in  the  Preface  to  the  former  edition. 

The  work  has  been  thoroughly  revised,  and  much  enlarged  in 
matter,  especially  by  the  addition  of  illustrative  cases,  largely 
American,  and  by  new  tests  and  methods  of  recovery  of  poisons 
from  organic  mixtures;  and,  also,  by  the  addition  of  an  entirely 
new  chapter  on  Gelsemium  poisoning,  and  an  Appendix  on  the 
Nature,  Detection,  and  Microscopic  Discrimination  of  Blood. 

Among  other  subjects  added  might  be  mentioned  Poisoning  by 
Potassium  Chlorate ;  Post-Mortem  Diffusion  of  Arsenic ;  Arsenic  in 
Medicines,  in  Fabrics,  and  in  Glass;*  Dragendorff's  method  for  the 
recovery  of  Vegetable  principles;  Nature  of  Ptomaines;  and  the 
preparation,  properties,  and  recovery  of  Jervine. 

The  chemical  nomenclature  of  the  former  edition  has  been  en- 
tirely revised  and  made  to  conform  with  the  more  recent  views  of 
chemists  on  that  subject. 

After  due  consideration,  it  was  concluded  to  retain  the  English 

*  The  glass  of  some  American  beakers  examined  since  the  text  on  this  sub- 
ject was  in  print  contained  0.34  per  cent,  of  metallic  arsenic. 


6  PEEFACE   TO   THE    SECOND    EDITION. 

system  of  weights  for  indicating  the  behavior  of  given  quantities  of 
the  different  poisons  with  reagents,  since  this  system  is  much  more 
familiar  to  lawyers  likely  to  consult  the  work,  and  even  to  most 
American  physicians  at  present,  than  the  metric  system.  To  the  pro- 
fessional chemist  it  matters  little  which  of  these  systems  of  weights 
is  employed  for  this  purpose.  If  the  reader  is  more  familiar  with 
metric  than  with  English  weights,  he  need  only,  after  reading  the 
fractions  employed  throughout  the  work  to  indicate  the  amount  of 
the  poison  or  substance  present,  substitute  the  word  solution  for  the 
word  "  grain,"  and  bear  in  mind  that,  unless  otherwise  stated,  the 
reaction  refers  to  the  behavior  of  about  0.0648  gramme  (one  grain) 
of  the  solution.     Thus,  for  yto  grain,  read  y^  solution. 

The  various  solutions  mentioned  throughout  the  text  are  equally 
readily  obtained  by  either  of  these  systems  of  weights,  by  dissolving, 
by  the  aid  of  an  acid  or  alkali  if  necessary,  one  part  (grain  'or 
gramme)  of  the  substance  in  one  hundred  parts  by  weight  of  water, 
when  what  is  known  as  a  1-1 00th  solution  will  be  obtained.  Ten 
parts  of  this  solution  mixed  with  ninety  parts  of  water  will  consti- 
tute a  1-lOOOth  solution.  And  ten  parts  of  the  last-named  solution 
with  ninety  of  water  will  form  a  l-10,000th  solution ;  that  is,  one 
part  by  weight  of  this  solution  will  contain  1-1 0,000th  of  its  weight 
of  the  substance  dissolved.  In  like  manner  solutions  in  any  other 
relative  proportion  may  be  prepared. 

In  determining  the  behavior  of  solutions  of  a  substance  with 
reagents,  it  is  necessary  to  observe  not  only  the  degree  of  dilution 
of  the  solution,  but  also  the  quantity  operated  upon.  Thus,  for  ex- 
ample, if  in  one  instance  only  a  single  drop  of  a  1-lOOth  solution 
is  employed,  whilst  in  another  one  hundred  times  that  quantity  of 
the  solution  is  used,  the  precipitate,  if  any  is  produced,  will  be  one 
hundred  times  greater  in  quantity  in  the  latter  than  in  the  former 
instance,  although  the  degree  of  dilution  is  the  same  in  both  in- 
stances. Similar  results  would  be  obtained  from  different  quantities 
of  like  solutions  of  all  strengths  until  the  degree  of  dilution  exceeded 


PREFACE    TO    TFIK    SErOXD    EniTIfjX.  7 

the  insolubility  of  the  substance  or  compound  produced  or  set  free 
by  the  reaijent,  when  no  quantity  of  the  solution,  no  matter  how 
great,  would  yield  any  precipitate  wiiatever.  Hence,  before  apply- 
ing reagents  the  solution  to  be  tested  should  he  concentrated  as  far 
as  practicable  with  the  application  of  the  tests  to  be  employed. 

Two  new  steel  Plates,  including  twelve  illustrations  of  micro- 
scopic crystals,  have  been  added  to  the  work.  These  illustrations, 
like  those  of  the  former  edition,  were  drawn  from  nature  and 
executed  upon  steel  by  her  to  whom  the  work  is  inscribed.  A  steel 
Plate  showing  the  apparent  size  of  the  red  corpuscles  of  the  blood 
of  six  different  mammals,  under  a  power  of  1150  diameters,  has 
also  been  added.  These  latter  illustrations  were  drawn  on  steel 
by  my  daughter,  Mrs.  J.  Marshall,  and  are  accurate,  on  the  steel, 
within  at  most  about  1-lOOOth  of  an  incii.  A  chromo-lithograph 
of  Blood-Spectra  and  some  wood-cut  illustrations  have  also  been 
added  to  the  work. 

The  author  would  here  ackuowledge  his  indebtedness  to  Dr, 
Leo  Mees,  formerly  his  assistant,  for  much  valuable  assistance  in 
collecting,  mounting,  and  in  the  measurement  of  the  corpuscles  of 
the  various  bloods  herein  considered. 


Uhivkksitt  of  Pbnsstlvania,  Philadelphia, 
March,  1885. 


TABLE    OF    CONTENTS. 


INTRODUCTION. 


Micro-Chemistry  of  Poisons,  Definition 

Application  of  the  Microscope 
Import  of  the  term  Poison 
Causes  modifying  the  action  of  Poisons 

1.  Idiosyncrasy 

2.  Habit 

3.  Disease 
Classification  of  Poisons 
Sources  of  Evidence  of  Poisoning 

I.  Evidence  from  the  Symptoms 

1.  The  Symptoms  occur  suddenly  . 

2.  They  rapidly  run  their  course  . 
Diseases  resembling  Poisoning  . 
Duties  of  Medical  Attendant 

II.   Evidence  from  Post-mortem  Appearances   . 

Appearances  rarely  characteristic  . 

Irritant  Poisons,  usual  effects  of    . 

Narcotic  Poisons 

Narcotico-Irritants  .... 

Appearances  common  to  Poisoning  and  Disease 

Redness  of  the  Stomach 

Softening  of  the  Stomach 

Ulceration  and  Perforation 
Points  to  be  observed  in  Post-mortem  Examination 
III.  Evidences  from  Chemical  Analysis 

Importance  of  Chemical  Evidence 

Substances  requiring  Analysis 

Precautions  in  regard  to  Analyses 

Failure  to  detect  Fatal  Quantity    . 

Value  of  individual  Chemical  Tests 

Failure  to  detect  Poison 

Of  Chemical  Reagents 

Of  Chemical  Apparatus  ..... 
Qualifications  of  the  Analyst  .... 


PAQE 

33 
34 
34 
35 
35 
35 
36 
37 
38 
38 
38 
41 
42 
42 
43 
43 
43 
44 
44 
,  44 
44 
45 


45 
46 
47 
47 
47 
48 
50 
50 
54 
56 
58 
58 


10 


TABLE   OF   CONTENTS. 


I]SrORGAE"IO    POISOI^S. 


CHAPTER   I. 

THE  ALKALIES:  POTASH,  SODA,  AMMONIA. 


General  Chemical  Nature 
Physiological  Effects 
Symptoms         .... 

1.  Of  the  Fixed  Alkalies 

2.  Of  Ammonia 
Period  when  Fatal 
Fatal  Quantity 

Treatment         .... 

Post-mortem  Appearances 

Nitrate  of  Potassium 

Chlorate  of  Potassium 

Tartrate,  Sulphate,  and  Oxalate  of  Potassium 

Chemical  Properties  of  the  Alkalies 

Distinguished  from  each  other 


Section  I. — Potassium  Oxide. 


General  Chemical  Nature         .... 
Density  of  Solutions  of  Potassium  Oxide 
Special  Chemical  Properties    .... 

1.  Chloride  of  Platinum  Test  . 

2.  Tartaric  Acid,  and  Sodium  Tartrate 

3.  Picric  Acid 

Other  Eeagents       .... 
Spectrum  Analysis 

Separation  from  Organic  Mixtures 
Quantitative  Analysis       ..... 


PAOE 

61 
61 
62 
62 
63 
64 
65 
66 
67 
69 
70 
72 
73 
73 


73 
74 

75 
76 
78 
80 
81 
82 
83 
84 


Section  II. — Sodium  Oxide. 

General  Chemical  Nature 
Density  of  Solutions  of  Soda  . 
Special  Chemical  Properties     .         . 
Coloration  of  Flame 

1.  Metantimoniate  of  Potassium  Test 

2.  Polarized  Light     . 
Behavior  with  Picric  Acid    . 

"  "      Tartaric   "      . 

"  "      Platinic  Chloride 

Separation  from  Organic  Mixtures 


84 
85 
85 
85 
85 
87 


89 


TABLE   OF   CONTENT8. 


11 


Section  III. — Ammonia. 


Genenil  Cliemical  Nutiiro 

Density  of  Solutions  of  Aminoniu  . 

Special  Cheniical  Propcrtios    . 

1.  Pliitinic  Chloriflo  Tost  . 

2.  Turtiiric  Acid  and  Tartrate  o 

3.  Picric  Acid 

4.  Nesslor's  Test 
Mercuric  Chloride 
Sonnenschein's  Test 

Separation  from  Organic  Mixtures 
Quantitative  Analysis 


f  Sodium 


PA 'IK 

89 
80 
'M) 
!)0 
01 
02 
93 
05 
95 
96 
96 


CHAPTER   II. 

THE   MINEKAL   ACIDS:   SULPHUEIC,    NITRIC,    HYDEOCHLORIC. 
General  Nature  and  Bffects 97 


Section  I. — Sulphuric  Acid. 


History 

Symptoms 

Period  when  Fat;il    . 

Fatal  Quantity 

Treatment 

Post-mortem  Appearances 

General  Chemical  Nature 

Density  of  Solutions  of  Sulphuric  Acid 

Special  Chemical  Properties  . 

1.  Chloride  of  Barium  Test 

2.  Nitrate  of  Strontium  . 

3.  Acetate  of  Lead  . 

4.  Veratrine     . 
Other  Reactions   . 

Separation  from  Suspected  Solutions 
Contents  of  the  Stomach 
From  Organic  Fabrics 

Quantitative  Analysis    . 


Section  II. — Nitric  Acid 

Symptoms 

Period  when  Fatal 

Fatal  Quantity 
Treatment 

Post-mortem  Appearances 
General  Chemical  Nature 
Density  of  Solutions  of  Nitric  Acid 


98 
98 
100 
101 
101 
102 
105 
106 
106 
107 
110 
111 
112 
112 
118 
116 
118 
118 


119 
121 
121 
121 
121 
123 
124 


12 


TABLE    OF    CONTEXTS. 


Special  Chemical  Properties 

1.  Copper  Test 

2.  Gold  Test     . 

3.  Iron  Test      . 

4.  Indigo  Test 
■5.  Brucine  Test 

6.  ISTarcotine  Test 

7.  Aniline  Test 
Iodine  and  other  Tests 

Separation  from  Organic  ilixtures 
Contents  of  the  Stomach 
From  Organic  Fabrics 

Quantitative  Analysis     . 


PAGE 

124 
125 
126 
127 
128 
129 
131 
182 
133 
134 
136 
136 
137 


Section  III. — Hydrochloric  Acid. 

Symptoms 138 

Period  when  Fatal 139 

Fatal  Quantity 140 

Treatment 141 

Post-mortem  Appearances      .         .         .         .         .         .         .         .         .         .  141 

General  Chemical  Nature       ..........  141 

Density  of  Solutions  of  Hydrochloric  Acid  .         .         .         .         .         .         .142 

Special  Chemical  Properties  ..........  143 

1.  Silver  Nitrate  Test 144 

2.  Xercurous  Nitrate       .........  14-5 

3.  Lead  Acetate 14-5 

Separation  from  Organic  Mixtures         ........  146 

Contents  of  the  Stomach 147 

From  Organic  Fabrics      .........  148 

Quantitative  Analysis     .         .         .         .         .         .         .         .         .         .         .148 

CHAPTER   III. 


OXALIC   AND   HYDROCYANIC    ACIDS   AND    PHOSPHOPvUS. 
Sectiox  I. — Oxalic  Acid. 

History  ..............     1-50 

Symptoms       .............     1-50 

Period  when  Fatal '.  .         .         .1-52 

Fatal  Quantity  .         .         .         .         .         .         .         .         .         .1-53 

Treatment •         ....     1-54 

Post-mortem  Appearances      .         .         .         .         .         .         .         .         .         .1.54 

General  Chemical  Nature       .         .         .         .         .         .         .         .         .         .     155 

Special  Chemical  Properties  .         .         .         .         .         .         .         .         .         .1-56 

1.  Silver  Nitrate  Test 157 

2.  Calcium  Sulphate         .         .         .         .         .         .         .         .         .1.58 

3.  Barium  Chloride .         .         .     159 


TABLE   OF   CONTENTS. 


13 


4.  Strontium  Nitrate 

6.  Lead  Acetate 

6.  Copper  Sulphate  . 
Separation  from  Organic  Mixtures 

Contents  of  the  Stomach  . 

The  Urine 
Quantitative  Anal3-sis    . 


Section  II. — Hydrocyanic  Acid. 


History  .... 
Symptoms 

Period  when  Fatal 

Fatal  Quantity 
Treatment 

Post-mortem  Appearances 
Chemical  Properties 
General  Chemical  Nature 
Special  Chemical  Properties 

1.  Silver  Nitrate 

2.  Iron  Test      . 

3.  Sulphur  Test 
Relative  Delicacy  of  these  Tests 
Other  Reactions   . 

Separation  from  Organic  Mixtures 
Examination  for  the  Vapor 
Method  by  Simple  Distillation 
Distillation  with  an  Acid 
From  the  Blood  and  Tissues 
Failure  to  detect  the  Poison 

Quantitative  Analysis    . 


Section  III. — PnosPHORrs. 


History  ......... 

Symptoms 

Period  when  Fatal 

Fatal  Quantity 

Treatment       ........ 

Post-mortem  Appearances      ..... 

Chemical  Properties       ...... 

General  Chemical  Nature 

Solubility 

Special  Chemical  Properties 

1.  Mitscherlich's  Method  for  Detection  . 

2.  Hydrogen  Method        .... 

3.  Lipowitz's       "  .         .         .         . 


Phosphoric  Acid 
General  Chemical  Nature 


PAOB 

160 
IGl 
162 
102 
164 
166 
166 


167 
168 
172 
173 
174 
175 
177 
177 
178 
178 
181 
184 
186 
187 
187 
188 
188 
189 
191 
192 
192 


193 
193 
195 
196 
197 
198 
199 
199 
200 
201 
202 
205 
207 

207 
207 


14 


TABLE    OF    CONTENTS. 


Special  Chemical  Properties  .... 

1.  Silver  Nitrate  Test 

2.  Magnesium  Sulphate   . 

3.  Molybdate  of  Ammonium  . 
Other  Eeactions  .... 

Separation  of  Phosphorus  from  Organic  Mixture 

Mitscherlich's  Method 

Lipowitz's  Method   .         . 

Dusart's  " 

Kecovery  as  Oxide  of  Phosphorus    . 

Failure  to  detect  the  Poison     . 
Quantitative  Analysis 


PAGE 

208 
208 
209 
210 
212 
212 
213 
214 
214 
215 
215 
216 


CHAPTER    IV. 

ANTIMONY. 

History 217 

Tartar  Emetic 217 

Symptoms 218 

Period  when  Fatal 219 

Fatal  Quantity 220 

Treatment 221 

Post-mortem  Appearances      .         . 221 

General  Chemical  Nature 222 

Solubility 222 

Special  Chemical  Properties 223 

1.  Sulphuretted  Hydrogen  Test 223 

2.  Acetate  of  Lead 225 

3.  Zinc  Test .         .         .225 

4.  Copper  Test 226 

5.  Antimonuretted  Hydrogen 227 

Action  of  the  Mineral  Acids 231 

"         "        Caustic  Alkalies 232 

Other  Pveactions '      .         .   '      .         .  233 

Separation  from  Organic  Mixtures "      .         .  233 

From  the  Tissues 236 

"       "     Urine .         .237 

Quantitative  Analysis 238 


CHAPTER   V. 

APvSENIC. 

I.  Metallic  Arsenic. 

History  and  Chemical  Nature 239 

Physiological  Effects 240 

Special  Chemical  Properties 240 

Compounds  of  Arsenic 241 


TABLE   OF   CXJNTEXTh. 


15 


II.  Arsenious  Oxide. — Arsenious  Acid 


History  nnd  Varictiis     . 
Symptoms 

Period  wlieii  Fatal 

Fatal  Quantity 
Treatment 
Post-mortem  Appearances 

Antiseptic  Properties 
General  Chemical  Nature 

Solubility 
Special  Chemical  Properties 
Of  Solid  Arsenious  Oxide 

Vaporization     . 

Sublimation 

Reduction 
Of  Solutions  of  Arsenious  Acid 

1.  Ammonio-Nitrate  of  Silver  Test 

2.  Ammonio-Sulphate  of  Copper 

3.  Sulphuretted  Hydrogen 

4.  Reinsch's  Test 

5.  Marsh's  Test 
Bloxam's  Method 

6.  Bettendorffs  Test 
Other  Reactions    . 

1.  Lime-water 

2.  Potassium  Iodide 

3.  Copper  Sulphate  and  Potassium  Hydrate 
Separation  from  Suspected  Solutions 

Vomited  Matters 
Contents  of  the  Stomach 
From  the  Tissues 
Fresenius  and  Babo's  Method 
Method  of  Gautier 

"      "  Danger  and  Flandin 
"      "  Duflos  and  Hirsch 
By  Distillation 
Boeke's  Method    . 
From  the  Urine 
Distribution  of  Absorbed  Arsenic 
Failure  to  Detect  the  Poison 
Detection  after  Long  Periods 
Post-mortem  Diflusion  of  Arsenic 
Arsenic  in  Chemicals,  Medicines,  and  Fabri 

"       "   Glass    . 
Quantitative  Analysis    . 


fAOE 

•-'41 
242 
246 
246 
247 
250 
251 
252 
253 
256 
256 
256 
257 
257 
260 
261 
263 
264 
271 
279 
293 
295 
296 
296 
296 
297 
297 
298 
299 
300 
301 
306 
307 
308 
308 
309 
309 
310 
312 
312 
313 
316 
319 
321 


16 


TABLE    OF   CONTENTS. 


III.  Arsenic  Oxide.— Arsenic  Acid. 


General  Chemical  Nature 
Physiological  Effects 
Special  Chemical  Properties  . 

1.  Sulphuretted  Hydrogen  Test 

2.  Ammonium-Copper  Sulphate 

3.  Silver  Nitrate 

4.  Keinsch's  Test 

5.  Ammonio-Magnesium  Sulphate 
Other  Eeactions    . 

Quantitative  Analysis    .... 


PAGE 

322 
322 
328 
323 
325 
326 
326 
327 
328 
328 


CHAPTER  VI. 


MEKCURY. 

General  Properties •         ■     330 

Physiological  Effects 330 

Combinations •        .         .         .         .     330 

Corrosive  Sublimate •     331 

Composition      ........•••     331 

Symptoms 331 

Period  when  Patal    .......-•■     335 

Fatal  Quantity 335 

Treatment •  •       ■         •         •         .336 

Post-mortem  Appearances 337 

General  Chemical  Nature 339 

Solubility '  •         ■         •         -339 

Special  Chemical  Properties 340 

In  the  Solid  State 340 

Of  Solutions  of  Corrosive  Sublimate 343 

1.  Ammonia  Test     ...  '. 343 

2.  Potassium  and  Sodium  Hydrates 344 

3.  Potassium  Iodide 345 

4.  Sulphuretted  Hydrogen 345 

5.  Stannous  Chloride •         .347 

6.  Copper  Test  .         .         ."        •         • 348 

7.  Silver  Nitrate       . 353 

Other  Eeagents •         •         ■         •         •     354 

Separation  from  Organic  Mixtures ■         .354 

Suspected  Solutions  .         ■ 355 

Vomited  Matters      . 356 

Contents  of  the  Stomach 356 

From  the  Tissues      .         . .358 

"        "   Urine 360 

Failure  to  Detect  the  Poison .361 

Quantitative  Analysis '^"'^ 


TARLK   OF   CONTENTS. 


17 


CHAPTP]ll   VII. 

LEAD,  COPPEll,   ZINC. 

Section  I. — Lkad. 


History  nnd  Chomical  Nnturp 
riiysiological  Effects 
Acetate  of  Lead 
Symptoms 

Chronic  Poisoning 

Period  when  Fatal 

Fatal  Quantity 
Treatment 

Post-mortem  Appearances 
General  Chemical  Nature 

Solubility 
Special  Chemical  Properties 
In  the  Solid  State  . 
Of  Solutions  of  Acetate  of  Lead 

1.  Sulphuretted  Hydrogen  Test 

2.  Sulphuric  Acid     . 

3.  Hydrochloric  Acid 

4.  Potassium  Iodide 

5.  Potassium  Chromate 

6.  Potassium  Hydrate  and  A 

7.  The  Alkaline  Carbonates 

8.  Ammonium  Oxalate     . 

9.  Zinc  Test      . 
Other  Pveagents     . 

Separation  from  Organic  Mixtures 
Contents  of  the  Stomach 
From  the  Tissues 
The  Urine 

Quantitative  Analysis    .         . 


PA  OP. 

ZP,?, 
3G4 
3G4 
364 
365 
366 
367 
367 
368 
368 
369 
369 
369 
370 
371 
372 
373 
374 
375 
376 
377 
377 
377 
378 
378 
379 
380 
381 
381 


Section  II. — Copper. 

History  and  Chemical  Nature 382 

Combinations   ...........  383 

Sulphate  of  Copper  and  Verdigris 383 

Physiological  Effects      ...........  383 

Symptoms       .............  384 

Period  when  Fatal 385 

Fatal  Quantity  .         . 386 

Treatment       .............  386 

Post-Mortem  Appearances     ..........  386 

2 


18  TABLE   OF   CONTENTS. 


PAGE 


Chemical  Properties ^°' 

In  the  Solid  State • ^^'^ 

Of  Solutions  of  Salts  of  Copper     .         .         . ^87 

1.  Sulphuretted  Hydrogen  Test 


2.  Ammonia 


390 


3.  Potassium  and  Sodium  Hydrates 391 

4.  Potassium  Ferrocyanide ^^^ 

5.  Iron  Test ^93 

6.  Platinum  and  Zinc  Test 393 

7.  Potassium  Arsenite •     •         •         •  394 

8.  Potassium  Chromate    .' ■     •         •         •  394 

9.  Potassium  Ferricyanide 395 

10.  Potassium  Iodide s         .         .         •  395 

Guaiacum  Test ,         .         .         .  396 

Detection  of  the  Acid -         •         •  396 

Separation  from  Organic  Mixtures 396 

Contents  of  the  Stomach           .         . 397 

Prom  the  Tissues 398 

The  Urine         .         .         •         •         • 399 

Quantitative  Analysis .         .  400 

Section  III. — Zinc. 

History  and  Chemical  Nature 400 

Sulphate  of  Zinc       .         .         .         .         - 402 

Chloride  of  Zinc       . 402 

409 
Symptoms 

Treatment 405 

Post-mortem  Appearances      .         .         .    ,     • 405 

Chemical  Properties  of  Salts  of  Zinc     .         .         ....         •         •         .406 

In  the  Solid  State 406 

When  in  Solution 407 

1 .  Sulphuretted  Hydrogen  Test 407 

2.  Potassium  Hydrate  and  Ammonia 408 

8.  Potassium  Perrocyanide 409 

4.  Potassium  Ferricyanide        ......••  409 

5.  Oxalic  Acid 410 

6.  Potassium  Chromate ■         •  410 

7.  Sodium  Phosphate 411 

Detection  of  the  Acid .         .         •         •         •         ■         •         ■         •  411 

Sopiiration  from  Organic  Mixtures          .....         .         •         •         ■  412 

Contents  of  the  Stomach 412 

From  the  Tissues       .         •         ■         ••,-.■         ■         ■         •  413 

.Quantitative  Analysis •         •     ,    •     .    •         •  413 


TABLE   OF   CONTENTS. 


1!) 


PA.RT    SKCOND. 

VEGETABLE    POISOIsrS. 


INTRODUCTION. 

PAOP. 

General  Nature  of  Vegetable  Poisons 417 

Separation  from  Complex  Organic  Mixtures  .         .  ...  418 

1.  Method  of- Stas 418 

2.  Kodgers  and  Girdwood's  Method 423 

3.  Method  of  Uslar  and  Erdmann 424 

4.  Process  of  Graham  and  Hoffmann      ......  426 

5.  Method  by  Dialysis 427 

6.  Dragendorff's  Method 429 

Ptomaines 431 


CHAPTER   I. 

VOLATILE   ALKALOIDS:    NICOTINE,    CONINE. 

Section  I. — Nicotine.     (Tobacco.) 

History   .... 
Preparation    . 
Symptoms 

Period  when  Fatal 

Fatal  Quantity 
Treatment 

Post-mortem  Appearances 
General  Chemical  Nature 

Solubility 
Special  Chemical  Properties 

1.  Platinic  Chloride  Test 

2.  Corrosive  Sublimate 

3.  Picric  Acid 

4.  Iodine  in  Potassium  Iodide 

5.  Auric  Chloride     . 

6.  Bromine  in  Bromohydric  Acid 

7.  Tannic  Acid 
Other  Reagents    . 

Separation  from  Organic  Mixtures 

Suspected  Solutions  and  Contents  of  the  Stomach 

From  the  Tissues 

From  the  Blood 

General  Method  of  Distillation 


434 
434 
435 
437 
438 
438 
438 
439 
439 
440 
441 
442 
444 
444 
445 
446 
446 
447 
447 
448 
450 
450 
452 


20 


TABLE   OF   CONTENTS. 


Section  II. — Conine.     (Conium  Maculatum.). 


History  .... 

Preparation    . 

Symptoms 

Treatment 

Post-mortem  Appearances 

General  Chemical  Nature 

Solubility 
Special  Chemical  Properties 

1.  Auric  Chloride  Test 

2.  Picric  Acid 
8.  Mercuric  Chloride 

4.  Iodine  in  Potassium  Iodide 

5.  Bromine  in  Bromohydric  Acid 

6.  Silver  Nitrate 

7.  Tannic  Acid 
Other  Keagents 
Fallacies 

Separation  from  Organic  Mixtures 


PAGE 

453 
453 
454 
455 
456 
456 
457 
457 
459 
460 
460 
460 
461 
462 
462 
462 
463 
464 


CHAPTER  II. 
OPIUM   AND   SOME   OP   ITS   CONSTITUENTS. 

I.  Opium. 

History  and  Chemical  Nature        . 466 

Symptoms 467 

Period  when  Fatal .         .         .469 

Fatal  Quantity .470 

Treatment .472 

Post-mortem  Appearances     ..........  474 

Physical  and  Chemical  Properties          .         . 475 

II.  Morphine. 

History  and  Preparation 476 

Symptoms 476 

Period  of  Death,  and  Fatal  Quantity 477 

Treatment  and  Post-mortem  Appearances     . 480 

General  Chemical  Nature 480 

Solubility 480 

Special  Chemical  Properties           .         .         . 483 

In  the  Solid  State 483 

Of  Solutions  of  Salts  of  Morphine 483 

1.  Potassium  and  Sodium  Hydrates         .                  .         .         .         .  483 

2.  Ammonia 484 

3.  Nitric  Acid 485 


TABLE   OF  CONTENTS. 


•21 


4.  Iodic  Acid    . 

5.  Ferric  Chloride    . 
0.  Sulpho-Molybdic  Acid 

7.  Potnssium  Iodide 

8.  Potnssium  Chromiite    . 

9.  Auric  Chloride     . 

10.  Platinic  Chloride 

11.  Iodine  in  Potnssium  Iodide 

12.  Bromine  in  Bromohydric  Acid 

13.  Picric  Acid 

14.  Chlorine  and  Ammonia 
Other  Keugents     . 
Kelative  Value  of  the  Preceding  Tests 


l-AOK 

48G 
487 
488 
490 
490 
491 
492 
492 
493 
493 
493 
494 
495 


III.  Meconic  Acid. 


History   ...... 

Preparation 

Physiological  Effects 
General  Chemical  Nature 

Solubility 
Special  Chemical  Properties  . 

1.  Ferric  Chloride  Test    . 

2.  Lead  Acetate 

3.  Barium  Chloride 

4.  Hj'drochloric  Acid 

5.  Silver  Nitrate 

6.  Potassium  Ferricyanide 

7.  Calcium  Chloride 
Other  Keagents     . 


SEPARATION    OF    MECONIC   ACID   AND    MOKPHINK    FROM    ORGAN 

Suspected  Solutions  and  Contents  of  the  Stomach 

Meconic  Acid  .... 

Morphine  .... 

Porphyroxine   .... 

Examination  for  Morphine  alone 
From  the  Tissues   ..... 

From  the  Blood 

The  Urine 

Failure  to  Detect  the  Poison 
Quantitative  Analysis  of  Morphine 


495 
495 
496 
496 
496 
497 
497 
499 
500 
501 
502 
502 
502 
503 


IC    MIXTURES. 


503 

504 
506 
509 
.510 
510 
511 
513 
513 
514 


IV.  Narcotine. 

History 515 

Preparation 515 

Physiological  Effects 516 


22  TABLE   OF   CONTENTS. 

PAGE 

Chemical  Properties       .......•••■  516 

1.  The  Alkalies  and  their  Carbonates 517 

2.  Sulphuric  Acid  and  Potassium  Nitrate        .         .         .         •         .518 

3.  Potassium  Acetate 519 

4.  Potassium  Chromate    ......•••  520 

5.  Potassium  Sulphocyanide 520 

6.  Auric  Chloride •         •         •  521 

7.  Iodine  in  Potassium  Iodide          .......  521 

8.  Bromine  in  Bromohydric  Acid    ,...-••  521 

9.  Potassium  Perrocyanide       ......■•  522 

10.  Picric  Acid 522 

Other  Eeagents    .         .         .         .         .         •         •         •         .         .  522 

V.  Codeine. 

History 523 

Preparation    .......••••••  523 

Physiological  Effects 523 

Chemical  Properties 524 

1.  The  Caustic  Alkalies 525 

2.  Iodine  in  Potassium  Iodide 526 

8.  Bromine  in  Bromohydric  Acid •         •  526 

4.  Potassium  Sulphocyanide 527 

5.  Potassium  Dichromate 527 

6.  Auric  Chloride 527 

7.  Platinic  Chloride •         •         •         .528 

8.  Picric  Acid •         •  528 

9.  Nitric  Acid  and  Potassium  Hydrate 528 

Other  Eeagents 528 

VI.  Narceine. 

History  and  Preparation         .....■■■■         k  529 

Physiological  Effects 529 

Chemical  Properties 529 

1.  Iodine  in  Potassium  Iodide  Test 531 

2.  Bromine  in  Bromohydric  Acid 531 

3.  Auric  Chloride 532 

4.  Platinic  Chloride •         .532 

5.  Picric  Acid 532 

6.  Potassium  Dichromate          .         .         .         •■        •         •         •         •  532 
Other  Eeagents •         •  532 

VII.  Opiantl. 

History  .         .         .         .         .         • 533 

Preparation 533 

Physiological  Effects 533 

Chemical  Properties       ...         .         , 533 

1.  Iodine  in  Potassium  Iodide  Test 534 


TARLE    OF    CON  I  KM  S.  23 


PAor. 


2.  Bromino  in  Bromohydric  Acid    ......  536 

3.  Sulphuric  Acid  and  Ilciit ^SS 

Other  Reagents •'jSO 

CHAPTER    II T. 
NUX   VOMICA,  STRYCHNINE,  BKUCINK. 

I.  Nux  Vomica. 

History  and  Composition        ..........  537 

Symptoms       .............  537 

Period  when  Fatal 539 

Fatal  Quantity 539 

Treatment 540 

Post-mortem  Appearances 540 

Chemical  Properties 541 

II.  Strychnine. 

History  and  Preparation 542 

Symptoms       ............  543 

Period  when  Fatal 549 

Fatal  Quantity .550 

Treatment 552 

Post-mortem  Appearances 555 

General  Chemical  Nature 557 

Solubility 558 

Special  Chemical  Properties ;         .         .  559 

In  the  Solid  State 559 

Of  Solutions  of  Strychnine    .         . 559 

1.  The  Caustic  Alkalies 561 

2.  Color  Test 562 

3.  Potassium  Sulphocyanide    .         .         -         .         .         .         .         .  575 

4.  Potassium  Iodide 575 

5.  Potassium  Bichromate         .         .         .         .         .         .         .         .  576 

6.  Auric  Chloride 578 

7.  Platinic  Chloride 579 

8.  Picric  Acid 580 

9.  Corrosive  Sublimate 581 

10.  Potassium  lodohydrargyrate 581 

11.  Potassium  Ferricyanide       ........  582 

12.  Iodine  in  Potassium  Iodide 588 

13.  Bromine  in  Bromohydric  Acid 584 

14.  Physiological  Test 584 

Other  Reagents 586 

Separation  from  Nux  Vomica         .........  586 

Suspected  Solutions  and  Contents  of  the  Stomach  ....  587 

Method  by  Dialysis 590 


24 


TABLE   OF    CONTENTS. 


From  the  Tissues 
The  Blood 
rrom  the  Urine 
Failure  to  Detect  the  Poison 
Quantitative  Analysis    . 


III.  Brucine. 

History  and  Preparation 
Physiological  Effects 
General  Chemical  Nature 

Solubility 
Special  Chemical  Properties  . 

1.  The  Caustic  Alkalies 

2.  Nitric  Acid  and  Stannous  Chloride     . 

3.  Sulphuric  Acid  and  Potassium  Nitrate 

4.  Potassium  Sulphocyanide 

5.  Potassium  Dichromate 

6.  Platinic  Chloride 

7.  Auric  Chloride     . 

8.  Picric  Acid  . 

9.  Potassium  Ferricyanide 

10.  Iodine  in  Potassium  Iodide 

11.  Bromine  in  Bromohydric  Acid 
Other  Keactions    . 

Separation  from  Organic  jVIixtures 


PAGE 

590 
593 
596 
597 
600 


600 
601 
601 
601 
602 
603 
603 
605 
605 
606 
607 
607 
608 
608 
609 
609 
609 
611 


CHAPTER    IV. 

ACONITINE,  ATEOPINE,  DATUEINE. 

Section  I. — Aconitine.     (Aconite.) 

History  and  Preparation 613 

Symptoms       .............  615 

Period  when  Fatal 617 

Fatal  Quantity 618 

Treatment 621 

Post-mortem  Appearances 623 

Chemical  Properties .  624 

Solubility 625 

Of  Solutions  of  Aconitine 625 

1.  The  Caustic  Alkalies .626 

2.  Auric  Chloride 626 

3.  Picric  Acid  .         . .627 

4.  Iodine  in  Potassium  Iodide 627 

5.  Bromine  in  Bromohydric  Acid 627 

Other  Reagents 628 

Fallacies  of  Preceding  Tests •  .         .628 

Physiological  Test 628 


TABI.E    OF    CONTENTS. 


25 


Separation  from  Organic  Mixtures         .... 

Siispcclod  Solutions  imd  Contents  uf  the  Stomaoli 
From  tlio  niodd 


PAOB 

'•.29 
•;29 

t;30 


Skction   [I. — Atropine.     (Belladonna.) 

History  ........ 

Preparation    ..... 

Symptoms        ....... 

Treatment       ....... 

Post-mortem  Ap]tt';n-aiR'o.<      .... 

Chemical  Properties       ..... 

Solubility 

Of  Solutions  of  Atropine       .... 

1.  The  Caustic  Alkalies    . 

2.  Bromine  in  Bromohydric  Acid  Test 

3.  Picric  Acid 

4.  Auric  Chloride     .... 

5.  Iodine  in  Potassium  Iodide 
Other  Reagents    .... 
Physiological  Test 

Separation  from  Organic  Mixtures 

From  the  Blood        .... 


631 
631 
633 
638 
639 
640 
640 
641 
641 
641 
642 
643 
643 
644 
645 
645 
647 


Section  III. — Daturine.     (Stramonium.) 


History  and  Preparation        ...... 

.     647 

Symptoms 

.     648 

Treatment 

:         .          .650 

Post-mortem  Appearances 

.     651 

Chemical  Properties 

.     651 

Separation  from  Organic  Mixtures         .... 

.     652 

CHAPTER    V. 

VERATRINE,    JERVINE,    SOLANINE. 

Section  I. — Veratrine.    Jervine.    (White  and  American  Helle- 
bores.) 

History  and  Preparation 653 

Symptoms. — Veratrum  Album 656 

Veratrum  Viride 657 

Veratrine 659 

Treatment 660 

Post-mortem  Appearances 660 

Chemical  Properties 660 

Solubility 662 


26 


TABLE    OF    CONTENTS. 


Of  Solutions  of  Veratrine 

1.  The  Caustic  Alkalies   . 

2.  Sulphuric  Acid  Test     . 

3.  Auric  Chloride     . 

4.  Bromine  in  Bromohydric  Acid 

5.  Iodine  in  Potassium  Iodide 

6.  Picric  Acid  . 

7.  Potassium  Dichromate 
Other  Eeagents     . 

Jervine,  Chemical  Properties 

In  Solid  State  . 

Of  Solutions  of  Jervine   . 
Separation  of  Veratrine  and  Jervine  from  Organic  Mixtures 

From  the  Blood 


PAGE 

662 
663 
663 
665 
665 
666 
666 
667 
667 
667 
668 
668 
670 
671 


Section  II. — Solanine.     (Nightshade.) 

History .672 

Preparation 672 

Symptoms 673 

Treatment 675 

Post-mortem  Appearances      ..........  675 

Chemical  Properties " 675 

Solubility 676 

Of  Solutions  of  Solanine 677 

1.  The  Caustic  Alkalies 677 

2.  Sulphuric  Acid  Test 678 

3.  Iodine  in  Potassium  Iodide 679 

4.  Potassium  Chromate '       •         •         •  679 

5.  Bromine  in  Bromohydric  Acid   .         ...         .         .         .  680 

Other  Eeactions 680 

Separation  from  Organic  Mixtures 681 


CHAPTER    VL 

GELSEMINE,     GELSEMIC     ACID.     (YELLOW  JESSAMINE.) 

History  and  Preparation        .         .         .......         .  683 

Gelsemine  ...........  683 

Gelsemic  Acid 684 

Physiological  Effects 684 

Symptoms 685 

Period  when  Fatal 687 

Fatal  Quantity  . 688 

Treatment       .         .         .         . 689 

Post-Mortem  Appearances     ..........  690 


TAHLK    OF    CONIKNIS. 

'   2ili 

'  IrXQK. 

Chemical  Properties 'il^l 

I.  Gelsemic  Acid      ...... 

.     09 1 

Solubility 

.    (;92 

Chemical  Reactions      .... 

.     092 

With  Acids 

.     692 

In  Solution       ..... 

.     693 

II.  Gelsemine 

.     694 

Solubility 

.     695 

Reactions  in  Solid  State  . 

.     695 

In  Solution 

.     696 

1.  Ammonia        .... 

.     696 

2.  Picric  Acid     .... 

.     696 

3.  Iodine  in  Potassium  Iodide    . 

.     697 

4.  Bromine  in  Bromobydric  Acid 

.     697 

5.  Auric  Chloride 

.     697 

6.  Platinic  Chloride  . 

.     697 

7.  Mercuric  Chloride 

.     G97 

Other  Reagents 

.     697 

Separation  from  Organic  Mixtures 

.     698 

a.  Gelsemic  Acid      ..... 

.     698 

b.  Gelsemine 

.     699 

From  the  Tissues 

.     699 

From  the  Blood 

.     700 

APPEI^DIX. 


BLOOD. 


PROPERTIES— DETECTION— DISCRIMINATION. 


.  General  Nature  of  Blood 

701 

Physical  Characters 

Composition 

Coagulation 

Corpuscles 

Non-Nucleated 

701 
701 
702 
702 
703 

Nucleated 

704 

Action  of  Water  and  Reagents  on  Corpuscles 

Circular  Corpuscles 

Oval               " 

705 
705 

706 

White  Corpuscles 

706 

Blood-Stains 

707 

28 


TABLE    OF    CONTENTS. 


II.  Chemical  Tests  for  Blood 

1.  Heat 

2.  Ammonia     ..... 

3.  Guaiacum  Test     .... 

4.  Hsemin  Crystals  .... 
Other  Eeactions  .... 

III.  Optical  Properties  of  Blood  . 

Micro-Spectroscope 
Blood-Spectra       .... 
Examination  of  Suspected  Stains 
Fallacies       ..... 

IV.  Microscopic  Detection  and  Discrimination 

Oviparous  Blood  .... 

Mammalian  Blood 

Limit  of  Determining  Differences 

By  Unaided  Eye    . 

By  Microscope 
Measurement  hy  the  Microscope 
Average  Size  of  Mammalian  Corpusc 
Distribution  for  Measurement 
Uniformity  in  Size 
Table  of  Average  Size 
Limit  of  Discrimination 
V.  Examination  of  Dried  Blood 
Liquids  Employed 
Kesults  Obtained 
Cases    . 
Fallacies 

Location  of  Stains 
Blood-Suckincj  Insects 


PA8E 

708 
708 
709 
709 
711 
713 
714 
714 
715 
718 
720 
721 
721 
723 
723 
723 
724 
725 
728 
728 
729 
733 
735 
737 
737 
738 
739 
739 
740 
741 


ILLUSTRATIONS. 


Chromo-Lithooraph  of  Blood-Spectra.     {Frontispiece.) 

UPON    STEEL. 


PLATE  I. 


Fig.  L  j^  grain  Potassium  Oxide,  as  nitrate  or  ctiloride,  -|-  Platinic  Chloride. 

2.  -j^  grain  Potassium  Oxide,  as  nitrate,  +  Tartaric  Acid. 

3.  ^-Q  grain  Potassium  Oxide,  as  chloride,  +  Sodium  Tartrate. 

4.  j^^  grain  Potassium  Oxide,  as  nitrate,  +  Picric  Acid. 

5.  Y^TS  grain  Ammonia,  as  ammonium  chloride,  +  Picric  Acid. 

6.  tJ*j  grain  Sodium  Oxide.  +  Picric  Acid. 

PLATE  IL 

Fig.  1.  ^-yoiF  grain  Sodium  Oxide,  -\-  Potassium  Metantimoniate. 

"     "^-  Tff  grain  Sodium  Oxide,  -}-  Tartaric  Acid. 

"    ^-  ttjW  grain  Sodium  Oxide,  as  chloride,  -|-  Platinic  Chloride. 

"    ^-  1^0  grain  Sulphuric  Acid,  -|-  Barium  Chloride. 

"     5.  Htdrofluosilicic  Acid, -f -Sariwm  CA^orirfe. 

"    ^-  TF(T  g^^^^  Sulphuric  Acid, +'S^^owi(iMW  lYt^ra^e. 

PLATE   III. 

■Y^  grain  Hydrochloric  Acid,  +  Lead  Acetate. 

TO'ws  grain  Oxalic  Acid,  on  spontaneous  evaporation. 

T^Vo"  grain  Oxalic  Acid,  -j-  Calcium  Chloride. 

yi^  grain  Oxalic  Acid,  -{-Barium  Chloride. 
"     ^-  TW  grain  Oxalic  Acid,  -\-  Strontium,  Nitrate. 
"     ^-  Tffrr  grain  Oxalic  Acid,  +  Lead  Acetate. 

PLATE  IV. 

Fig.  1.  xrj 00  grain  Hydrocyanic  Acid  vapor,  +  Silver  Nitrate. 
"    ^-  1 6  6^0  6  0  grain  Hydrocyanic  Acid  vapor,  -f-  Silver  Nitrate. 
"     ^-   10^0  0  grain  Phosphoric  Acid,  +  Ammonium,  Magnesium  Sulphate. 
"    4.  Tartar  Emetic,  from  hot  supersaturated  solution. 
"     5.  Arsenious  Oxide,  sublimed. 
"     6.  -j^  grain  Arsenious  Oxide,  -{-Ammonium  Silver  Nitrate. 

29 


IG 

1. 

11 

2. 

(1 

3. 

Cl 

4. 

30  ILLUSTEATIONS    UPON    STEEL. 


PLATE   V. 

Fig.  1.  Y-Qo  grain  Arsenic  Oxide,  -\-  A^jiTnonium  Magnesium  Sulphate. 

2.  Corrosive  Sublimate,  sublimed. 

3.  y^  grain  Lead,  -f-  diluted  Sulphu7nc  Acid. 

4.  yig-  grain  Lead,  -f-  diluted  Hydrochloric  Acid. 

5.  ■ij^Vs'  grain  Lead,  +  Potassium  Iodide. 

6.  Yo^o  o'  grain  Zinc,  +  Oxalic  Acid. 

PLATE   VL 

Fig.  1.  j^  grain  Nicotine,  -j-  Platinic  Chloride. 

2.  Yo^  grain  Nicotine,  -|-  Corrosive  Sublimate. 

3.  x^Vo  grain  Nicotine,  -|-  Picric  Acid. 

4.  Conine,  pure,  -f-  vapor  of  Hydrochloric  Acid. 

5.  Yo^  grain  Conine,  -j-  Picric  Acid. 

6.  Y^  grain  Morphine,  -\-  Potassium  Hydrate. 

PLATE   VIL 

Fig.  1.  ^ho  grain  Morphine,  -f-  Potassium,  Iodide. 

2.  j-Iq-  grain  Morphine,  +  Potassiw>n  Chrom,ate. 

3.  Y^  grain  Morphine,  +  Platinic  Chloride. 

4.  ^^  grain  Meconic  Acid,  -j-  Barium  Chloride. 

5.  Yho  gi'^in  Meconic  Acid,  +  Hydrochloric  Acid. 

6.  YTo  grain  Meconic  Acid,  -|-  Potassium  Ferricyanide. 


Fig.  1. 
2. 
3. 
4. 
5. 
6. 


PLATE   VII L 

yig  grain  Meconic  Acid,  -|-  Calcium  Chloride. 
ToVo  grain  Narcotine,  -\-  Potassium  Hydrate. 
yip  grain  Narcotine,  -f-  Potassium  Acetate. 
yig  grain  Codeine,  -j-  Iodine  in  Potassium  Iodide. 
yi^  grain  Codeine  Iodide,  from  alcoholic  solution, 
-i-g.  grain  Codeine,  +  Potassium  Sulphocyanide. 


PLATE  IX. 

Fig.  1.  -j-^Q^  grain  Codeine,  +  Potassium  Dichromate. 

2.  yig-  grain  Codeine,  -f-  Potassium  Iodide. 

3.  y-J^  grain  Narceine,  +  Iodine  in  Potassium  Iodide. 

4.  ^^  grain  Narceine,  -f-  Potassium,  Dichromate. 

5.  ^1^  grain  Opianyl,  ~\-  Iodine  in  Potassium  Iodide. 

6.  .^ig.  grain  Opianyl,  +  Bromine  in  Bromohydric  Acid. 

PLATE   X. 

J^IG.  1.  .j^  grain  Strychnine,  -|-  Potassium  Hydrate  or  Annmonia. 

2.  j-ig  grain  Strychnine,  +  Potassium  Sulphocyanide. 

3.  .^^  grain  Strychnine,  +  Potassium  Dichromate. 

4.  -^L^  grain  Strychnine,  +  Potassium  Dichromate. 

5.  ^^^  grain.  Strychnine,  +  -^wric  Chloride. 

6.  yJg-^  grain  Strychnine,  +  Platinic  Chloride. 


ILLUSTRATIONS    UPON    STKKF,.  31 


TLATK    XI. 

Fio.  \.  ^-^f^f^  giiiin  Strychnine,  +  Picric  Add. 

2.  .j-Jj  grain  Strychnine,  -(-  Corrosive  Sublimate. 

3.  yjj  grain  Stkychnink,  +  Potassium  Ferricyanide. 

4.  y^5j  grain  Stkychnink,  -|-  todine  in  Potassium  Iodide. 

5.  1^  grain  Brucink,  -}-  Potassiuin  Hydrate  or  Ammonia. 

6.  ^^  grain  Brucine,  -f-  Potassium  Sulphocyanide. 

PLATE   XII. 

Fig.  L  yjj  grain  Brucine,  +  Potassium.  Dichromate. 

2.  xA^Tf  grain  Brxtcine,  +  Platinic  Chloride. 

3.  y-Ju  grain  Brucine,  +  Potassium  Ferricyanide. 

4.  ^ijj  grain  Atropine,  +  Potassium  Hydrate  or  Ammonia. 

5.  ^1^  grain  Atropine,  +  Bromi^ie  in  Bromohydric  Acid. 

6.  xryJwc  gr^iii  Atropine,  -f-  Bromine  in  Bromohydric  Acid. 

PLATE  XIIL 

Fiii.  ].  yjjj  grain  Atropine,  -j-  Picric  Acid. 

2.  yIt)  grain  Atropine,  +  Auric  Chloride. 

3.  ^hf)  grain  Veratrine,  +  Auric  Chloride. 

4.  ^^  grain  Veratrine,  +  Bromine  in  Brom.ohydric  Acid. 

5.  SoLANiNE,  from  alcoholic  solution. 

6.  yi_  grain  Solanine,  as  sulphate,  on  spontaneous  evaporation. 

PLATE   XIV. 

Fig.  1.   j-^  grain  Morphine,  +  Iodine  in  Potassium  Iodide. 

2.  Y^jj  grain  Morphine,  +  Potassium  lodohydrar gyrate. 

3.  Jertine,  from  ethereal  solution. 

4.  .j^  grain  Jervine,  +  Sulphuric  Acid. 

5.  y-J-j  grain  Jervine,  -}-  Nitric  Acid. 

6.  Jervine,  from  blood  of  cat. 

PLATE   XV. 

Fig.  1.  Gelsemine  Hydrochloride. 
"    2.  Gelsemic  Acid,  from  ethereal  solution. 
"    3.  Gelsemic  Acid,  sublimed. 

"     4.  -j-j^  grain  Gelsemic  Acid,  -(-  Sulphuric  Acid,  then  Ammonia 
"    5.  H^MATix  Hydrochloride. 
"    6.  H^MATiN  Hy'drochloride,  from  -i^  grain  of  blood. 

PLATE   XV L 

Fig.  1.  Blood-Corpuscles  of  Man,  x  1150  diameters. 


"    2.       " 

"     Dog,  X 

"    3. 

"  Mouse,  X 

"     4. 

Ox,  X 

'  •     5.        " 

"  Sheep,  X 

''     (j.        " 

"     Goat,  X 

MICRO-CHEMISTRY  OF  POISONS. 


INTEODUOTION. 

definition;    application    of    the  microscope IMPORT   OF    THE    TERM 

POISON  ;  modifying  circumstances — classification  OF  poisons 

— sources  of  evidence  of  poisoning:  evidence  from 

symptoms — from  post-mortem  appearances — 

FROM  chemical  ANALYSIS. 

By  the  terra  Micro-Chemistry  of  Poisons,  we  under.stand  the 
study  of  the  cheraical  properties  of  poisons  as  revealed  by  the  aid  of 
the  raicroscope.  Although  the  scope  of  the  present  work  is  not  limited 
to  this  department  of  the  subject,  yet,  as  that  branch  of  the  science 
forms  a  main  element  of  the  treatise,  we  have  designated  it  by  that 
title. 

The  instrument  requisite  for  investigations  of  this  kind  may  be 
comparatively  simple ;  and  but  little  accessory  apparatus  will  be  re- 
quired. The  stage  of  the  instrument  should  be  sufficiently  large  to 
receive  a  watch-glass  having  a  diameter  of  not  less  than  two  inches. 
Object-glasses  of  only  low  power  are  usually  required.  Very  often 
an  amplification  of  from  thirty  to  forty  diameters  will  answer  the 
purpose  best,  but  more  frequently,  perhaps,  a  power  of  about  seventy- 
five  .will  be  the  most  satisfactory,  while  in  some  few  instances  an 
amplification  of  about  two  hundred  and  fifty  will  be  required.  The 
objectives  best  suited  for  these  powers  are  the  inch  and  a  half,  two- 
thirds  inch,  and  one-fifth  inch,  respectively.  In  these  investigations, 
as  in  all  others  with  the  microscope,  the  lowest  amplification  that  will 
reveal  the  true  character  of  the  object  examined  will  be  the  most  satis- 
factory. A. polarizing  apparatus  will  sometimes  be  necessary  to  deter- 
mine the  true  nature  of  an  object ;  and  in  some  instances  a  micromete)' 
will  be  found  useful  to  ascertain  the  absolute  size  of  the  object. 

3  33 


34  INTRODUCTION. 

In  applying  the  microscope  to  the  examination  of  the  result  of  a 
chemical  reagent  upon  a  suspected  solution,  a  single  drop  of  the  liquid, 
placed  in  a  watch-glass  or  upon  a  glass  slide,  is  treated  with  a  very 
small  quantity  of  the  reagent,  added  by  means  of  a  pipette,  and  the 
mixture,  with  as  little  agitation  as  possible,  transferred  to  the  stage  of 
the  instrument.     If,  as  is  sometimes  the  case,  the  crystalline  deposit 
produced  by  the  reagent  be  readily  broken  up  by  agitation,  the  watch- 
glass  containing  the  drop  of  fluid  to  be  examined  is  placed  on  the 
stage  of  the  instrument  before  the  addition  of  the  reagent.    In  many 
instances,  as  will  be  noticed  hereafter,  the  formation  of  a  precipitate 
is  much  facilitated  by  stirring  the  mixture  with  a  glass  rod.    Should 
the  mixture  evolve  fumes  injurious  to  the  object-glass,  a  flat  watch- 
glass  having  a  ground  edge  is  selected,  and  this  is  covered  by  a  piece 
of  very  thin  glass.     Any  special  directions  in  regard  to  the  use  of 
this  instrument  will  be  pointed  out  hereafter,  as  occasion  may  require. 
A  Poison  is  any  substance  which,  when  taken  into  the  body  and 
either  being  absorbed  or  by  its  direct  chemical  action  upon  the  parts 
with  which  in  contact,  or  when  applied  externally  and  entering  the 
circulation,  is  capable  of  j)roducing  deleterious  eifects.     There  is  no 
doubt  that  all  poisons  are  to  a  greater  or  less  extent  absorbed  into  the 
circulation.     In  fact,  with  most  of  them  this  is  certainly  a  condition 
essential  to  the  production  of  their  effects ;    yet  it  would  appear  that 
in  the  action    of   some   substances,   which    produce   local   chemical 
changes,  death,  in  some  instances  at  least,  can  be  referred  only  to 
the  effects  of  the  changes  thus  produced.     The  mineral  acids  and 
caustic  alkalies  are  the  principal  poisons  which  have  a  direct  chemical 
action  upon  the  parts  with  which  they  are  brought  in  contact.    This 
action  is  due  to  a  mutual  affinity  existing  between  the  agent  and  the 
tissue.     In  this  respect,  the  action  of  these  substances  differs  from 
that  of  certain  heated  liquids,  such  as  boiling  water,  which  are  inert 
at  ordinary  temperatures,  but  which,  simply  on  account  of  their  con- 
dition, induce  a  chemical  change  in  the  part  to  which  they  are  ap- 
plied, without  themselves  being  chemically  concerned  in  the  change. 
When  applied  externally,  some  poisons  are  absorbed  by  simply  being 
brought  in  contact  with  the  unbroken  skin  ;  whilst  others  do  not  enter 
the  circulation  unless  applied  to  an  abraded  or  wounded  surface. 

Poisons  differ  greatly  in  regard  to  the  quantity  necessary  to  prove 
injurious.  Thus,  the  fiftieth  part  of  a  grain  of  aconitine  has  seriously 
endangered  the  life  of  an  adult,  while,  on  the  other  hand,  an  ounce  of 


CAUSES   MODIFYIN(t    THE    ACTION    OF    POISONS.  35 

magnesium  sulphate  may  generally  be  administered  with  impunity  ; 
yet  in  large  quantities  the  latter  suhstanee  has  in  several  instances 
caused  death,  and  is  strictly  a  poison,  although  not  commonly  reputed 
as  such.  As  yet  we  know  of  no  substance  that  is  poisonous  in  every 
proportion.  Any  of  the  most  powerful  poisons  may  be  administered 
in  certain  quantities  without  producing  any  ai)preciable  effect,  and 
most  of  them  may  be  so  employed  as  to  constitute  valuable  remedial 

agents. 

In  medico-legal  inquiries,  the  leading  idea  connected  with  the 
term  poison  is  whether  the  given  results  are  directly  traceable  to  the 
substance  and  the  intention  with  which  it  was  employed. 

Poisons  not  only  diifer  from  each  other  in  regard  to  the  quantity 
necessary  to  destroy, life,  but  the  effects  of  the  same  substance  may 
be  much  modified  by  circumstances,  and  even  substances  which  to 
most  persons  are  harmless  may,  on  account  of  certain  peculiarities  of 
constitution,  produce  deleterious  effects. 

Cau.ses  which  modify  the  effects  of  Po/son.s.— Among  the  causes 
which  may  modify  the  effects  of  poisons,  may,  in  this  connection, 
be    mentioned   Idiosyncrasy,  Habit,  and  a  Diseased   State  of  the 

System. 

1.  Idiosyncrasy,  or  a  peculiarity  of  constitution,  may  variously 
modify  the  effects  of  substances.  Thus,  in  some  persons  ordinary 
medicinal  doses  of  certain  drugs,  such  as  opium  or' mercury,  produce 
violent  symptoms,  and  even  death.  In  other  instances,  substances 
which  to  most  persons  are  harmless,  and  even  ordinary  articles  of 
food,  produce  symptoms  of  irritant  poisoning.  This  has  been  ob- 
served in  the  eating  of  certain  kinds  of  fish,  honey,  pork,  veal,  and 
mutton.  In  still  another  form  of  idiosyncrasy,  there  is  a  diminished 
susceptibility  to  the  action  of  certain  substances  which  to  most  per- 
sons are  active  poisons.  This  peculiarity  of  constitution  is  very 
rare,  and  is  most  generally  observed  in  regard  to  the  action  of  mer- 
cury and  opium.  Dr.  Christison  relates  an  instance  in  which  a 
gentleman,  unaccustomed  to  the  use  of  opium,  took  without  injury 
nearly  an  ounce  of  good  laudanum. 

2.  Habit  may  render  certain  poisons  harmless  in  doses  which 
to  most  persons  would  prove  rapidly  fatal.  The  influence  of  habit 
is  daily  seen  in  the  use  of  opium,  tobacco,  and  alcohol ;  and  it  is 
well  known  that  certain  other  agents  when  administered  medicinally, 
in  frequently-repeated  doses,  after  a  time  lose  their  ordinary  effects. 


36  rNTRODUCTio]sr. 

Persons  accustomed  to  the  use  of  opium  have  taken  daily,  for  long 
periods  together,  quantities  of  laudanum  that  Avould  prove  fatal  to 
several  persons  unaccustomed  to  its  use.  Although  this  influence 
has  principally  been  observed,  as  remarked  by  Dr.  Christison,  in 
regard  to  the  action  of  certain  organic  poisons,  especially  such  as 
act  on  the  brain  and.  nervous  system,  yet  it  seems  now  to  be  fully 
established  that  certain  persons  in  Styria  accustom  themselves  even  to 
the  eating  of  arsenic  in  doses  of  several  grains  daily,  and  continue 
the  practice  for  many  years  without  experiencing  any  of  the  usual 
eifects  of  the  poison.  The  statements  formerly  made  by  Dr.  Tschudi 
and  others  in  regard  to  the  existence  of  this  practice  have  been  dis- 
credited by  most  writers  on  toxicology ;  but  the  accounts  more  re- 
centlv  published  by  Dr.  Roscoe,  as  quoted  by  Dr.  Taylor  [Jled.  Jur., 
Amer.  ed.,  1861,  693),  and  the  direct  observations  of  Dr.  Maclagan, 
of  Edinburgh  (Chemieal  Xews,  London,  July,  1865,  36j,  while  on  a 
visit  to  Styria,  seem  to  leave  no  doubt  whatever  of  its  existence.  In 
one  of  the  cases  observed  by  Dr.  Maclagan,  the  individual,  a  muscu- 
lar young  man,  aged  twenty-six  years,  swallowed,  in  connection  with 
a  very  small  piece  of  bread,  five  grains  of  genuine  powdered  arseni- 
ous  oxide,  or  white  arsenic,  which  he  stated  was  about  the  quantity 
he  was  in  the  habit  of  taking  twice  a  week.  In  the  urine  passed  by 
this  individual  two  hours  afterward,  as  also  in  that  passed  after 
twenty-six  hours.  Dr.  Maclagan  detected  a  very  notable  quantity  of 
arsenic.  It  is  but  proper  to  observe  that  the  experience  of  most 
medical  practitioners  in  the  use  of  this  substance  does  not  accord 
with  the  results  of  this  Styrian  practice. 

3.  Disease. — In  certain  diseased  conditions  of  the  system,  there 
is  a  diminished  susceptibility  to  the  action  of  certain  poisons ;  whilst 
in  others,  there  is  an  increased  susceptibility,  even  to  the  action  of 
the  same  substance.  Thus,  in  tetanus,  hydrophobia,  mania,  and  de- 
lirium tremens,  quantities  of  opium  which  in  ordinary  states  of  the 
system  would  be  fatal  may  often  be  administered  with  beneficial 
eifects.  In  a  case  of  tetanus  related  by  Dr.  A\^atson  {Praotioe  of 
Physic),  something  over  four  ounces  of  laudanum  was  taken  on  an 
average  daily,  for  twenty  days ;  after  which  the  patient  recovered. 
The  same  writer  quotes  another  instance  of  the  same  affection,  in 
which  an  ounce  of  solid  opium  was  taken,  in  divided  doses,  daily, 
for  twenty-two  days.  So  also,  in  inflammation  of  the  lungs,  enormous 
doses  of  tartar  emetic  have  been  given  with  advantage.     On  the 


CLASSIFICATION    OF    I'OISONS.  37 

other  hand,  in  cases  in  which  there  is  a  predisposition  to  apoplexy, 
an  ordinary  dose  of  opium  may  cause  death.  In  like  manner,  in 
certain  diseases,  there  is  an  increased  suscej)til)ility  to  the  action  of" 
mercury  and  dthcr  minei-al  suhstancps. 

Classification  of  Poisons. — Poisons  may  bo  arranged,  accord- 
ing to  the  symptoms  they  produce,  under  three  classes, — namely,  Ir- 
ritants, Narcotics,  and  Narcotico-Irritants.  Since,  however, 
there  are  many  poisons  the  effects  of  which  are  subject  to  great 
variation,  and  others  which  according  to  their  ordinary  effects  might 
with  equal  propriety  be  placed  in  one  or  another  of  these  classes, 
this  classification  is  open  to  much  objection. 

Irritant  Poisons,  as  a  class,  produce  irritation  and  inflamma- 
tion of  the  stomach  and  bowels,  attended  or  followed  by  intense  pain 
in  these  parts,  tenderness  of  the  abdomen,  and  violent  vomiting  and 
purging,  the  matters  evacuated  being  often  tinged  with  blood.  Some 
of  the  members  of  this  class,  such  as  the  mineral  acids  and  caustic 
alkalies,  also  possess  corrosive  properties,  and  accordingly  occasion, 
in  addition  to  the  effects  just  mentioned,  more  or  less  disorganization 
of  the  mouth,  throat,  oesophagus,  and  stomach.  The  action  of  these 
substances,  if  not  too  dilute,  is  immediate,  and  is  attended  with  a 
sense  of  burning  heat  in  the  parts  with  which  they  come  in  contact. 
When  highly  diluted,  any  of  the  corrosive  poisons  may  act  by  simply 
inducing  irritation  and  inflammation. 

The  irritant  poisons  may  be  divided  into  three  sections,  according 
to  the  kingdom  of  nature  to  which  they  belong, — namely,  mineral, 
vegetable,  and  animal.  The  first  section  is  much  the  largest,  and 
embraces,  with  the  exception  of  some  gaseous  substances,  all  strictly 
inorganic  poisons.  Gamboge  and  cantharides  are,  respectively,  ex- 
amples of  the  second  and  third  sections. 

Narcotic  or  Cerebral  Poisons  are  such  as  act  principally 
on  the  brain  and  spinal  marrow,  more  especially  on  the  former. 
They  induce  headache,  vertigo,  stupor,  impaired  vision,  delirium, 
insensibility,  paralysis,  convulsions,  and  coma.  This  class  contains 
comparatively  few  substances,  the  principal  of  which  are  opium  and 
hydrocyanic  acid.  Several  of  the  poisonous  gases  belong  to  this 
class. 

Narcotico-Irritants  partake,  as  indicated  by  their  name,  of 
the  action  of  both  the  preceding  classes.  Thus,  they  may  produce, 
as  a  result  of  their  irritant  action,  nausea,  pain   in  the  stomach, 


38  INTRODUCTION. 

vomiting,  and  purging;  and  as  a  result  of  their  action  on  the  nervous 
system,  stupor,  delirium,  paralysis,  coma,  and  convulsions.  Some 
of  them,  however,  do  not  usually  produce  well-marked  symptoms  of 
irritation  ;  and  all  of  them  produce  their  most  marked  effects  on  the 
nervous  system.  A  few,  such  as  strychnine  and  brucine,  act  chiefly  on 
the  spinal  cord,  and  produce  violent  tetanic  convulsions,  without  any 
other  prominent  symptom.  Hence  these  have  been  termed  the  Con- 
vukives  or  Spinal  poisons.  All  the  members  of  this  general  class, 
which  is  quite  numerous,  are  derived  from  the  vegetable  kingdom. 

In  referring  the  symptoms  in  a  given  case  to  the  action  of  either 
of  the  above  classes,  it  must  not  be  forgotten,  as  already  intimated, 
that  the  members  of  each  do  not  always  produce  the  same  effects. 
Thus,  arsenic  has  occasioned  symptoms  similar  to  those  of  narcotic 
poisoning ;  whilst  opium  has  produced  effects  resembling  poisoning 
by  an  irritant. 

Sources   of   Evidence   of   Poisoning. 

The  medical  evidence  in  cases  of  poisoning  is  derived  chiefly 
from — 1.  The  symptoms;  2.  The  post-moiiem  appearances ;  and,  3. 
Chemical  analysis. 

1 .  Evidence  from  the  Symptoms. 

In  forming  an  opinion  in  a  case  of  suspected  poisoning,  the  medi- 
cal examiner  should  acquaint  himself  with  not  only  the  special 
character  of  the  symptoms  present,  but  also,  as  far  as  practicable, 
the  previous  health  and  habits  of  the  patient,  when  food  or  drink 
was  last  taken,  whether  in  taking  it  any  peculiar  taste  or  odor  was 
observed,  and  whether  others  partook  of  the  same  food. 

Among  the  characters  of  the  symptoms  of  poisoning  usually 
mentioned  by  writers  on  this  subject,  the  most  constant  are — 1.  The 
symptoms  arise  suddenly,  and  soon  after  the  taking  of  food,  drink, 
or  medicine ;  and,  2.  They  rapidly  prove  fatal. 

1.  The  symptoms  occur  suddenly,  and  soon  after  the  taking  of  some 
solid  or  liquid. — The  greater  number  of  poisons,  when  taken  in 
fatal  quantity,  manifest  their  action  either  immediately  or  within  a 
short  period,  the  symptoms  of  but  few  being  delayed,  under  ordinary 
circumstances,  much  beyond  an  hour.  Many  instances  might  be 
cited  in  which  a  knowledge  of  the  time  that  elapsed  between  the 
taking  of  food  or  drink  and  the  appearance  of  the  suspected  symp- 


SVMI'TOM.S    A.S    KVIUKNCE   OF    I'OISONING.  39 

toins  wiis  ill  itself  .sutticicnt  to  deterniiiie  that  tliey  wore  really  <lue 
to  natural  eaiiscs  and  not  to  tlu;  effects  of"  poison.  In  considering 
this  relation,  however,  it  must  n(»t  be  overlooked  that  the  interval 
between  the  taUini;  of  a  poison  and  the  first  appearance  of  symptoms 
not  only  varies  with  each  substance,  but  the  time,  as  well  as  the  char- 
acter of  the  symptoms  of  the  same  poison,  may  be  more  or  less 
affected  by  circumstances,  such  as  quantity,  the  state  in  which  ad- 
ministered, condition  of  the  stomach,  combination  with  other  sub- 
stances, and,  as  already  mentioned,  a  diseased  state  of  the  system. 
Thus,  strychnine,  when  taken  in  fatal  quantity,  has  produced  violent 
symj>toms  within  five  minutes  afterward,  and  they  usually  appear 
within  thirty  minutes;  yet  they  have  been  delayed,  in  one  instance  at 
least,  for  three  hours.  It  is  well  known  that  antimony,  arsenic,  lead, 
and  various  other  poisons,  when  taken  into  the  system  in  repeated 
small  doses,  may  give  rise  to  effects  wholly  different  from  those 
usually  produced  by  a  single  poisonous  dose  of  the  substance. 

As  a  general  rule,  poisons  act  more  speedily  when  taken  in  the 
state  of  solution  than  in  the  solid  form.  On  the  other  hand,  a  full 
stomach,  and,  according  to  Dr.  Christison,  sleep,  may  delay  the  ac- 
tion of  certain  substances.  That  the  action  of  one  poison  may  be 
modified  by  the  presence  of  another,  is  well  illustrated  by  the  follow- 
ing case.  A  man,  aged  twenty-nine  years,  swallowed  three  grains 
of  strychnine,  one  drachm  of  opium,  and  an  indefinite  quantity  of 
quinine.  When  seen  by  a  physician  ticelve  hours  afterward,  he  only 
complained  of  feeling  "  queer."  But  there  was  extreme  cerebral 
excitement;  the  pulse  quick,  full  and  strong;  pupils  contracted;  the 
whole  face  of  a  deep-red  color ;  tongue  tremulous  and  covered  with 
a  brownish-white  fur ;  surface  of  the  body  hot,  with  profuse  perspira- 
tion ;  body  and  limbs  in  violent  tremor,  and  at  intervals  spasmodic 
action  of  all  the  muscles,  alternating  with  comparative  quiet  and 
drowsiness,  from  which  he  was  easily  roused.  Upon  the  administra- 
tion of  full  emetic  doses  of  zinc  sulphate,  opium  was  freely  ejected. 
One  hour  later,  the  patient  became  quite  drowsy,  but  when  roused 
would  start  violently  and  remain  delirious  for  some  minutes.  In 
two  hours  more,  complete  stupor  suddeuly  supervened,  and  continued, 
with  but  little  change,  till  death,  which  occurred  forty  hours  after  the 
mixture  had  been  taken.  [Chicago  Jledieal  Journal,  November, 
1860.)  How  far  the  first  appearance  and  character  of  the  symptoms 
of  a  particular  poison  may  depart  from  their  ordinary  course,  can  be 


40  INTRODUCTION. 

learned  only  from  a  comparison  of  well-authenticated  cases.  In  this 
respect,  our  knowledge  at  present  in  regard  to  the  effects  of  very 
many  substances  is  extremely  limited,  and  there  is  no  reason  to  be- 
lieve that  in  regard  to  any  we  have  as  yet  met  with  the  greatest 
deviation  possible. 

In  this  connection,  it  must  also  be  borne  in  mind  that  there  are 
certain  natural  diseases,  the  symptoms  of  which  resemble  more  or 
less  those  of  poisoning,  and  which  may  appear  suddenly  at  any  time. 
In  fact,  some  of  these  diseases,  such  as  apoplexy  and  perforation  of 
the  stomach,  are  more  likely  to  occur  soon  after  the  taking  of  food 
than  at  any  other  period.  Instances  of  this  kind,  however,  are  of 
rare  occurrence,  and  the  subsequent  history  of  the  case  will  usually 
enable  the  practitioner  to  determine  without  difficulty  its  true  nature. 
Nevertheless,  cases  have  occurred,  the  nature  of  which  could  be  estab- 
lished only  by  the  post-mortem  appearances  and  chemical  analysis. 

When  two  or  more  persons  who  have  eaten  of  the  same  food 
are  suddenly  seized  with  violent  symptoms,  there  is,  of  course, 
increased  reason  for  suspecting  the  presence  of  a  poison.  This  cir- 
cumstance has  in  some  instances  at  once  revealed  the  source  of  the 
poison.  Results  of  this  kind,  however,  may  be  due  to  an  unwhole- 
some or  diseased  condition  of  the  food ;  or  to  its  having  accidentally 
become  contaminated  with  a  poisonous  metal,  such  as  copper,  lead, 
or  zinc,  during  its  preparation.  On  the  other  hand,  several  persons 
may  partake  of  the  same  meal,  or  even  of  the  same  food,  and  poison 
have  been  designedly  introduced  only  into  the  portion  intended  for 
a  particular  individual.  Thus,  in  a  case  in  which  we  were  consulted, 
and  which  will  be  referred  to  hereafter,  a  family  of  several  persons 
having  mush  and  milk  for  supper,  the  mush  was  placed  on  the  table 
in  one  dish,  while  the  milk  was  distributed  at  the  usual  places  of 
sitting,  in  bowls.  Into  one  of  the  bowls  strychnine  had  been  intro- 
duced, and  its  intensely  bitter  taste  was,  perhaps,  the  only  circum- 
stance that  saved  the  life  of  the  person  for  whom  it  was  intended; 
only,  however,  to  become  the  victim  a  few  days  afterward  of  a  fatal 
quantity,  under  a  form  in  which  its  taste  was  entirely  concealed.  In 
another  instance,  the  plum-pie  served  for  dinner  was  furnished  to 
the  several  members  of  the  family,  on  separate  plates ;  under  the 
crust  of  one  of  the  pieces,  arsenic  had  been  placed,  and  proved  fatal 
to  the  person  who  ate  it.  From  what  has  already  been  stated,  it  is 
obvious  that  several  persons  may  even  partake  of  the  same  poisoned 


SYMrTOMS    AS    EVIDEXCE   OF    POISONING.  U 

food,  and  the  results  be  very  dilVereiit.  \h\  llcrk  quotes  several 
striking  examples  of  this  kind. 

Lastly,  in  inquiries  of  this  kind  it  must  be  remembered  that 
poisons  may  be  introduced  into  the  system  in  other  ways  tlian  with 
food,  drink,  or  medicine.  Thus,  jioisoninj;  by  the  external  applica- 
tion of  the  substance  is  not  of  unfrecjuent  occurrence;  the  same  is 
also  true  of  the  inhalation  of  certain  vapors  and  gases.  Instances 
of  this  kind,  however,  are  usually  the  result  of  accident.  Several 
instances  are  recorded,  in  which  jwisons  were  criminally  introduced 
into  the  rectum  and  vagina;  and  Dr.  Christison  cites  a  case  in  which 
a  fiital  quantity  of  suli>huric  acid  was  poured  into  the  mouth  of  an 
individual  while  asleep. 

2.  The  symptoms  rapidly  rim  their  course. — The  duration  of  the 
symptoms  of  poisoning,  like  their  appearance,  is  subject  to  great 
variation,  even  with  regard  to  the  same  substance.  Some  few  poisons, 
as  hydrocyanic  acid,  nicotine,  and  conine,  usually  prove  fatal  within 
a  few  minutes,  and  most  of  them  within  comparatively  short  periods. 
Yet,  as  just  intimated,  great  differences  have  been  observed  even  in 
regard  to  the  action  of  the  same  substance.  Thus,  the  fatal  period 
of  hydrocyanic  acid  poisoning  has  been  protracted  for  several  hours ; 
whilst,  on  the  other  hand,  arsenic,  which  on  an  average  perhaps 
does  not  prove  fatal  in  less  than  twenty-four  hours,  has  caused  death 
in  less  than  two  hours.  As  a  general  result,  a  large  -dose  of  a  given 
substance  will  prove  more  rapidly  fatal  than  a  small  one,  yet  this  is 
by  no  means  always  the  case.  Half  a  grain  of  strychnine  has  caused 
the  death  of  an  adult  in  less  than  twenty  minutes,  while  in  a  case  in 
which  between  five  and  six  grains  were  taken,  death  was  delayed  for 
six  hours ;  and  even  larger  quantities  than  the  last  mentioned  have 
been  followed  by  recovery. 

The  vegetable  poisons  as  a  class,  usually,  either  prove  fatal  within 
at  most  a  very  few  days,  or  the  patient  entirely  recovers ;  but  many 
of  the  mineral  substances  frequently  do  not  cause  death  until  after 
the  lapse  of  several  days.  In  fact,  many  of  the  members  of  the 
latter  class  may  give  rise  to  secondary  effects  which  may  extend 
through  an  interval  of  many  weeks,  or  even  months.  The  usual 
period  within  which  each  of  the  more  common  poisons  proves  fatal, 
and  how  far  it  has  departed  from  its  ordinary  course,  will  be  pointed 
out  hereafter  in  the  special  consideration  of  the  individual  substances. 

In  considering  the  duration  of  the  symptoms  in  a  case  of  suspected 


42  INTEODUCTION. 

poisoning,  it  must  be  remembered  that  the  symptoms  of  some  natural 
diseases  not  onlj  closely  resemble  those  of  certain  kinds  of  poison- 
ing, but  also  run  their  course  with  equal  rapidity.  In  most  instances, 
however,  a  careful  examination  of  the  symptoms,  with  a  full  history 
of  the  case,  when  this  can  be  obtained,  will  enable  the  medical  prac- 
titioner to  form  a  correct  diagnosis ;  but  cases  not  unfrequently  occur 
the  true  nature  of  which  can  be  established  only  by  the  post-mortem 
a*ppearances  and  chemical  analysis. 

The  diseases  most  likely  to  give  rise  to  symptoms  resembling  irri- 
tant poisoning  are,  cholera,  inflammation  of  the  stomach  and  bowels, 
and  perforation  of  the  stomach  ;  and  those  that  may  simulate  narcotie 
poisoning — apoplexy,  inflammation  of  the  brain,  and  organic  diseases 
of  the  heart.  Cholera  has  been  mistaken  for  poisoning  by  arsenic, 
and,  on  the  other  hand,  arsenical  poisoning  has  been  mistaken  for 
that  disease.  The  same  has  also  been  true  in  regard  to  apoplexy 
and  opium  poisoning.  The  symptoms  of  disease  of  the  heart,  in  the 
rapidity  of  their  action,  may  closely  resemble  the  effects  of  hydro- 
cyanic acid  and  of  nicotine.  The  true  nature  of  some  of  the  fore- 
going diseases  is  readily  revealed  upon  dissection  ;  but  others,  like 
the  poisons  with  whose  symptoms  they  may  be  confounded,  leave  no 
well-marked  morbid  appearances. 

In  the  examination  of  a  case  of  suspected  poisoning,  the  medical 
attendant  should  obtain  as  far  as  possible  a  full  history  of  the  progress 
of  the  symptoms  and  their  relation  to  the  taking  of  food,  drink,  or 
medicine.  All  suspicious  articles  of  this  kind  should  be  collected ; 
and  if  vomiting  has  occurred,  the  matters  ejected  should  also  be  col- 
lected and  their  character  noted.  All  articles  thus  obtained  should 
be  carefully  sealed,  if  solid,  in  clean  white  paper,  and  if  liquid,  in 
clean  glass  jars,  distinctly  labelled,  and  preserved  for  future  examina- 
tion, the  collector  being  careful  not  to  permit  any  such  article  to  pass 
out  of  his  possession  until  delivered  to  the  proper  person. 

A  chemical  examination  of  some  of  these  articles  may  at  once  re- 
veal the  true  nature  of  the  symptoms.  It  need  hardly  be  remarked 
that  a  failure  to  discover  poison  under  these  circumstances  will  by 
no  means  be  conclusive  evidence  that  a  poison  had  not  been  taken. 
On  the  other  hand,  the  detection  of  poison  in  a  remnant  of  food  or 
medicine  taken  by  the  person  will  not  of  itself  be  conclusive  proof 
that  a  poison  had  been  taken.  Symptoms  of  poisoning  have  been 
feigned  and  poison  put  into  articles  of  this  kind  for  the  purpose  of 


MORBID   APPEAKANCES   OF    POISONING.  43 

charging  another  with  an  attempt  to  murder.  Tlie  existence  of  this 
tact  can,  oi'  course,  be  determined  only  by  the  attending  circumstances. 
Some  years  since  we  were  engaged  in  a  case  in  which  it  clearly  ap- 
pearetl  that  a  man  maliciously  put  a  large  quantity  of  white  arsenic 
into  an  alcoholic  medicine  he  was  using,  and  actually  swallowed  suffi- 
cient of  the  mixture  to  produce  serious  symj)toms ;  lie  tiien  charged 
his  wife  with  the  poisoning. 

2.  Evidence  from  Post-mortem  Appearances. 

There  are  very  few  instances  in  which  the  post-mortem  ap- 
pearances are  peculiar  to  ])oisoning.  Nevertheless,  this  part  of  the 
evidence  should  always  be  very  carefully  considered,  for  when  taken 
in  connection  with  the  symptoms  and  other  circumstances,  it  may 
fully  establish  the  true  character  of  a  case  which  would  otherwise 
be  doubtful.  In  death  from  natural  disease,  a  post-mortem  examina- 
tion may  at  once  discover  the  fact.  However,  appearances  of  ordi- 
nary disease  may  be  present,  and  death  have  resulted  from  the  effects 
of  poison.  Several  instances,  in  which  coincidences  of  this  kind  ex- 
isted, might  be  cited.  The  presence  of  some  few  poisons,  as  opium 
and  hydrocyanic  acid,  may  sometimes  be  recognized  by  their  odor ; 
and  others,  when  in  the  stomach,  by  their  color  or  botanical  char- 
acters. It  is  a  popular  belief  that  great  lividity  of  the  body  and 
rapid  decomposition  always  attend  and  are  characteristic  of  death 
from  poisoning ;  but  these  results  are  rarely  produced,  and  are  by 
no  means  peculiar. 

Some  poisons  leave  no  appreciable  morbid  changes  in  the  dead 
body ;  and  of  those  that  usually  do,  the  appearances  are  subject  to 
great  variety,  and  in  many  instances  similar  to  the  effects  of  ordinary 
disease,  or  even  the  results  of  cadaveric  changes.  The  mineral  acids 
and  caustic  alkalies  usually  leave  the  most  marked  evidence  of  their 
action,  and  in  some  instances  this  is  quite  characteristic. 

The  irritant  poisons  as  a  class  usually  produce  irritation  and 
inflammation  of  one  or  more  portions  of  the  alimentary  canal,  the 
effects  being  sometimes  confined  to  the  stomach,  while  at  other  times 
they  extend  to  a  greater  or  less  degree  throughout  the  entire  canal. 
In  some  instances  the  coats  of  the  stomach  become  ulcerated  and 
softened,  and  even  perforated.  Poisons  of  this  class,  however,  may 
cause  death  without  leaving  any  discoverable  change  in  the  body. 
This  has  been  the  case  even  in  respect  to  some  of  the  more  acrid  and 


44  INTEODUCTIOJSr. 

corrosive  substances.  In  several  instances  of  poisoning  by  arsenic, 
which  generally  produces  strongly  marked  appearances  in  the  stomach 
and  bowels,  nothing  abnormal  was  found  upon  dissection.  In  the 
minute  examination  of  the  tissues  of  the  alimentary  canal,  M.  Bailloa 
advises  the  inspection  to  be  made  under  transmitted  light. 

Narcotic  poisons  in  some  instances  produce  more  or  less  distention 
of  the  veins  of  the  brain,  but  in  others  they  leave  no  marked  morbid 
appearances,  and  in  none  are  the  appearances  peculiar.  According 
to  Orfila,  the  lungs  almost  always  present  livid  and  black  spots,  and 
their  texture  is  more  dense  and  less  crepitant.  These  appearances, 
however,  may  result  from  ordinary  causes.  In  some  few  instances 
there  has  been  more  or  less  irritation  of  the  alimentary  canal ;  but 
this  condition  was  most  probably  induced  by  the  vehicle  in  which 
the  poison  was  taken,  or  by  the  remedies  subsequently  administered. 

Narcotico-irritants  partake  in  the  nature  of  their  effects  of  both 
the  preceding  classes.  Thus,  they  may  produce  irritation  and  even 
ulceration  of  portions  of  the  alimentary  canal,  and  congestion  of 
the  lungs  and  of  the  veins  of  the  brain  and  its  membranes.  But  in 
most  instances  the  morbid  changes  are  not  well  marked. 

The  usual  morbid  changes  produced  by  the  individual  poisons 
will  be  pointed  out  hereafter ;  but  in  this  connection  may  be  briefly 
mentioned  some  of  the  appearances  which  may  be  equally  produced 
by  ordinary  disease  or  cadaveric  changes  and  by  poisoning. 

Appearances  common  to  Poisoning  and  Disease. — Redness  of  the 
stomach  and  intestines  as  the  effect  of  poisoning,  cannot  in  itself  be 
distinguished  from  that  arising  from  natural  disease.  This  condition 
is  not  only  frequently  the  result  of  active  disease,  but  it  has  often 
been  observed  immediately  after  death  in  cases  in  which  during  life 
there  were  no  indications  of  derangement  of  the  stomach  or  bowels. 
Moreover,  various  pathologists  have  observed  that  pseudo-morbid 
redness  of  the  mucous  membrane  of  the  stomach  sometimes  makes 
its  appearance  several  hours  after  death.  Dr.  Christison  is  of  the 
opinion  that  an  effusion  under  the  villous  coat  of  the  stomach,  and 
incorporation  with  its  substance,  of  dark  brownish-black  blood,  is 
characteristic  of  violent  irritation,  if  not  of  the  effects  of  poison 
alone.  It  is  well  known  that  colored  substances  within  the  stomach, 
and  the  contact  of  this  organ  after  death  with  the  adjacent  parts, 
may  cause  it  to  become  more  or  less  colored.  But  these  appearances 
are  readily  distinguished  from  the  effects  of  poison. 


MORBID    APPEARANCES    OF   POISONING.  45 

Softening  of  the  stomach  is  another  appearance  which  may  give 
rise  to  embarrassment.  When  dne  to  the  action  of  poison,  it  is 
usnally  acconii)anii'(l  hy  other  a|)pearanccH  winch  readily  distingnislj 
it  from  the  effects  of  ordinary  disease  or  post-mortem  changes.  Dr. 
Carswell  has  sliown  that  this  condition  is  not  unfreqnently  ])roduced 
by  the  chemical  action  of  the  gastric  jnice  after  death.  lie  also 
observes  tliat  in  softening  of  the  mucous  membrane  of  the  stomach 
as  the  result  of  inflannnatory  action,  the  tissue  is  always  more  or 
less  opaque,  and  the  action  attended  by  one  or  more  of  the  products 
of  this  pathological  state;  whereas  in  post-mortem  softening,  the 
tissue  is  always  transparent,  and  the  action  never  attended  with  serous 
effusion  or  other  concomitants  of  inflammation. 

Ufceixition  and  perforation  of  the  stomach  arc  not  unfreqnently 
produced  by  corrosive  poisons,  but  they,  especially  tlic  latter,  are 
rarely  met  with  as  the  result  of  the  action  of  the  simple  irritants. 
As  the  effect  of  natural  disease  or  post-mortem  action,  they  are  not 
uncommon.  In  many  instances  these  appearances,  as  the  result  of 
poisoning,  can  be  distinguished  from  those  arising  from  other  causes 
only  by  a  history  of  the  symptoms  during  life,  or  by  the  detection  of 
poison  in  the  tissues  or  other  parts  of  the  body.  This  distinction  is 
usually  well  marked  in  the  action  of  the  mineral  acids  and  caustic 
alkalies. 

Perforation  of  the  stomach  has  not  uufrequently  occurred  from 
gelatinization  of  its  tissues,  and  in  cases  in  which  during  life  there 
was  no  evidence  of  a  diseased  state  of  that  organ.  These  appear- 
ances have  been  chiefly  observed  in  cases  of  violent  or  sudden  death. 
It  was  formerly  believed  that  this  condition  was  always  a  morbid 
process,  and  characteristic  of  a  special  disease.  But,  since  the  re- 
searches of  modern  pathologists  have  shown  that  the  gastric  juice 
has  the  property  of  dissolving  the  dead  stomach,  and  that  many  of 
these  lesions  have  undoubtedly  been  due  to  the  action  of  that  fluid 
after  death,  there  is  little  doubt  that  they  may  all  be  referred  to 
post-mortem  changes.  When  the  gastric  juice  escapes  through 
the  aperture  thus  produced,  it  may,  as  has  often  been  the  case,  exert 
its  solvent  action  upon  the  adjacent  organs.  As  these  appearances 
are  unattended  by  signs  of  irritation,  they  are  usually  readily  dis- 
tinguished from  the  effects  of  poisoning.  Should,  however,  a  per- 
foration of  this  kind  occur  in  a  case  in  which  prior  to  death  the 
stomach  was  affected  with  signs  of  irritation,  it  might  be  impossible 


46  INTEODUCTION. 

from  the  appearances  alone  to  determine  the  true  character  of  the 
perforation. 

Perforation  of  the  oesophagus  and  of  the  intestines,  as  the  result 
of  poisoning,  is  not  at  all  likely  to  occur.  In  fact,  there  seems  to  be 
only  one  instance  of  the  former,  and  none  of  the  latter,  on  record. 
But  these  conditions,  as  the  result  of  disease,  have  often  been  ob- 
served ;  and  they  have  even  resulted  from  the  action  of  the  gastric 
juice  after  death. 

Points  to  he  observed  in  post-mortem  examinations. — All  investiga- 
tions of  this  kind  should  be  made  in  the  presence  of  the  proper  law 
officer;  and  it  is  well  for  the  examiner  to  have  the  assistance  and 
corroboration  of  another  physician.  All  appearances  observed, 
whether  abnormal  or  otherwise,  should  be  fully  written  down  at  the 
time  of  their  observance.  The  length  of  time  the  person  has  been 
dead ;  how  long  he  survived  the  first  symptoms ;  and  the  condition 
of  the  body  in  respect  to  external  appearances,  should  as  far  as  prac- 
ticable be  learned  and  carefully  noted.  In  the  dissections,  the  con- 
dition of  the  entire  alimentary  canal,  and  of  all  the  organs  essential 
to  life,  should  be  minutely  examined ;  in  the  female,  the  vagina 
and  uterus  should  also  be  inspected.  The  stomach  with  its  contents, 
and  a  portion  of  the  small  intestines,  properly  ligatured,  should  be 
removed  from  the  body.  The  condition  of  these  organs,  and  the 
nature  of  their  contents,  may  then  be  examined.  In  some  instances, 
however,  it  is  best  not  to  open  these  organs  until  they  are  delivered 
to  the  chemist.  A  portion  of  the  liver  and  of  the  blood  should  also 
be  removed  for  chemical  analysis.  And  in  some  instances  it  is  im- 
portant to  remove  other  parts  of  the  body,  as  the  kidneys,  spleen, 
heart,  and  brain,  and  even  portions  of  the  muscles,  for  chemical 
examination. 

All  the  organs  and  the  blood  thus  removed  should  be  collected  in 
separate,  clean  glass  vessels,  great  care  being  taken  that  none  of  the 
reserved  substances  at  any  time  be  brought  in  contact  with  any  sub- 
stance that  might  afterward  give  rise  to  suspicion.  Before  passing 
out  of  the  sight  of  the  examiner,  the  bottles  should  be  securely  sealed 
and  fully  labelled.  They  should  then  be  retained  in  his  sole  possession 
until  delivered  to  the  proper  person. 


VALUK  OF  <'IIF:MI('AL   axalvsis.  ,  47 

.').  J'Audencc  J'roni   Chcmicdl  Analjixix. 

Importance  of  chemical  evidence. — In  most  charges  of"  poisoning, 
the  final  issue  depends  ii[)on  the  results  of  the  chemical  analysis. 
In  fact,  in  many  instances  in  which  the  evidence  from  symptoms, 
post-mortem  appearances,  and  moral  circumstances  is  very  equivocal 
or  in  part  wanting',  a  chemical  examination  may  at  once  determine 
the  true  cause  of  death.  It  must  be  remembered,  however,  that  a 
person  may  die  from  the  effects  of  poison  and  not  a  trace  of  its  ])res- 
ence  be  discoverable  in  any  part  of  the  body ;  while,  on  the  other 
hand,  the  mere  discovery  of  a  poison  in  the  food  or  drink  taken  or 
in  the  body  after  death,  is  not  in  itself  positive  proof  that  it  occasioned 
death. 

It  has  been  claimed  that  a  failure  to  detect  poison  in  the  dead 
body,  by  proper  chemical  skill,  was  evidence  that  death  was  the 
result  of  some  other  cause;  but  this  claim  is  entirely  groundless. 
The  symptoms  and  pathological  appearances,  at  least  in  connection 
with  moral  circumstances,  are  often  sufficient  in  themselves  fully  to 
establish  death  from  poisoning ;  and  a  number  of  convictions  have 
very  properly  been  based  on  these  grounds  in  instances  in  which 
chemical  evidence  was  ^vanting,  and  even  when  it  had  entirely  failed. 
There  are  a  number  of  organic  poisons  which  at  present  cannot  be 
recognized  by  chemical  tests;  and  instances  are  recorded  in  which 
death  resulted  from  large  quantities  of  some  of  the  poisons  most 
easy  of  detection,  and  not  a  trace  could  be  discovered  in  any  part 
of  the  body.  It  is  obvious  that  the  discovery  of  minute  traces  of 
such  poisons  as  are  used  medicinally  could  not,  independently  of 
symptoms  and  other  circumstances,  be  regarded  as  evidence  of  poi- 
soning. 

Substances  requiring  analysis. — The  substances  that  may  directlv 
become  the  subject  of  a  chemical  analysis,  in  a  case  of  suspected 
poisoning,  are  :  the  pure  poison  in  its  solid  or  liquid  state ;  suspected 
articles  of  food  or  medicine;  matters  ejected  from  the  body  by 
vomiting  or  purging;  the  urine;  suspected  solids  found  in  the 
stomach  or  intestines  after  death ;  the  contents  of  the  stomach  or 
bowels;  any  of  the  soft  organs  of  the  body,  as  the  liver,  spleen, 
etc. ;  and  the  blood. 

Sometimes  it  is  only  necessary  to  examine  one  of  the  above- 
mentioned  substances ;  but  in  many  instances  two  or  more  of  them 


48  INTRODUCTION. 

require  examination.  If  a  poison  be  thus  detected,  it  will  sometimes 
become  necessary  to  examine  substances  other  than  those  specified, 
in  order  to  determine  its  real  source.  The  evidence  of  poisoning  is, 
of  course,  most  complete  when  the  poison  is  recovered  from  some  of 
the  soft  organs  of  the  body,  after  it  had  been  absorbed.  So,  also, 
the  proof  will  be  more  direct  when  the  poison  is  detected  in  the 
contents  of  the  stomach  or  intestines,  than  in  articles  of  food  or 
medicine. 

Precautions  in  regard  to  analyses. — When  called  to  make  a  chemi- 
cal examination  of  any  suspected  material,  the  analyst  should  obtain, 
as  far  as  practicable,  a  knowledge  of  the  symptoms,  and,  if  death 
has  taken  place,  of  the  post-mortem  appearances,  observed  in  the 
suspected  case :  since  these,  when  known,  will  generally  enable  him 
to  decide  at  least  to  which  class  of  poisons  the  substance  belongs,  and 
in  some  instances  will  even  indicate  with  considerable  certainty  the 
individual  substance.  He  may  thus,  by  following  these  indications 
in  the  analysis,  save  much  labor,  and — which  in  many  instances  is 
of  much  more  importance — be  enabled  fully  to  establish  the  presence 
of  poison  when  present  in  quantity  too  minute  to  be  recognized  under 
other  circumstances.  It  must  not  be  forgotten,  however,  that  irritant 
poisons  have  produced  symptoms  resembling  those  induced  by  some 
of  the  narcotics,  and  that  the  latter  may  produce  symptoms  of  irritant 
poisoning. 

So,  also,  before  applying  any  chemical  test  to  a  suspected  solid  or 
liquid,  its  quantity — of  the  former  by  weight,  and  of  the  latter  by 
measure — should  be  accurately  determined.  In  the  application  of 
the  reagents,  the  very  least  quantity  of  the  material  that  will  answer 
the  purpose  should,  at  least  at  first,  be  employed  for  each  test.  In 
like  manner,  in  the  preparation  of  complex  mixtures,  the  residual 
solution  should  be  reduced  to  the  very  smallest  volume  compatible 
with  the  application  of  the  tests  that  it  may  become  necessary  to 
apply.  There  is  little  doubt  that  in  many  of  the  reported  instances 
of  non-detection  of  poisons  the  failures  have  resulted  from  a  neglect 
of  this  point.  It  should  always  be  borne  in  mind  that  a  given 
quantity  of  a  poison,  when  in  solution  in  a  small  quantity  of  fluid, 
may  yield,  with  a  given  reagent,  perfectly  characteristic  results, 
whereas  if  the  solution  be  but  slightly  more  dilute,  the  reaction  may 
entirely  fail.  Thus,  the  hundredth  part  of  a  grain  of  nicotine  in  one 
grain  of  water  yields  with  platinic  chloride  a  copious  and  rather 


VALUE   OF   CHKMICAL    ANALYSIS.  49 

characteristic  crystalline  precipitiite,  wliilo  the  .siinic  (jiiaiititv  in  fen 
grains  of  that  liquid  yields  no  j)reci])itate  whatever. 

In  the  preparation  of  the  contents  of  the  stoniaeli  and  (if  the 
solid  organs  of  the  body,  it  is  often  advisable  to  employ  oidy  ;ibunt, 
one-half  or  two-thirds  of  the  matter  for  the  first  examination.  This 
proportion  will  perhaps  in  all  cases,  at  least  in  regard  to  mineral 
poisons,  suffice  to  show  the  poison  if  present,  while  in  case  of  acci- 
dent the  analysis  could  be  repeated.  When,  however,  the  analyst 
has  perfect  confidence  in  his  ability  to  go  safely  through  with  the 
examination,  it  is  perhaps  best  not  to  make  this  division  of  matter, 
at  least  in  the  investigation  for  certain  organic  poisons.  The  minute 
quantity  of  poison  usually  taken  up  by  the  blood,  especially  in  the 
case  of  the  alkaloids,  renders  it  necessary  to  operate  upon  compara- 
tively large  quantities  of  this  fluid,  and  to  conduct  the  examination 
with  extreme  care. 

When  the  symptoms  or  attending  circumstances  do  not  point  to 
a  particular  poison,  or  at  least  to  the  class  to  which  it  belongs,  it  is 
obvious  that  a  division  of  the  matter  submitted  for  examination 
becomes  absolutely  necessary.  Under  these  circumstances,  great  care 
should  be  exercised  not  to  subject  the  matter  to  any  process  that 
would  preclude  the  possibility  of  examining  for  any  poison  for  which 
it  might  afterward  become  necessary  to  look. 

It  need  hardly  be  observed  that  during  investigations  of  this  kind 
the  examiner  should  never  lose  sight  of  the  suspected  material,  except 
when  it  is  in  some  secure  place ;  and  the  greatest  possible  care  should 
be  taken  that  it  is  not  brought  in  contact  with  any  substance  the 
nature  of  which  is  not  fully  understood.  A  neglect  of  these  direc- 
tions may  prove  fatal  to  the  results  of  a  chemical  examination.  The 
careful  analyst  need  not  be  cautioned  against  hasty  conclusions  in 
regard  to  the  results  of  reagents. 

After  the  presence  of  a  poison  is  fully  established,  it  is  in  most 
instances  only  necessary  to  be  able  to  state  the  probable  amount 
present;  but  sometimes  it  is  necessary  to  determine  its  exact  quantity. 
In  all  cases  in  which  it  is  practicable,  it  is  best  to  determine  the 
actual  amount  recovered ;  but  it  not  unfrequently  occurs,  especially 
in  the  detection  of  absorbed  poison,  that  the  quantity  present  is  so 
small  as  not  to  admit  of  a  direct  quantitative  analysis.  Under  these 
circumstances,  we  may  often,  by  accurately  noting  the  volume  of 
solution  obtained  and  observing  the  comparative  reaction  of  several 

4 


50  INTEODU€TION. 

tests,  estimate  very  closely  the  strength  of  the  solution,  and  from 
this  deduce  within  narrow  limits  the  amount  of  the  poison  present. 

It  was  formerly  claimed  that  unless  a  quantity  of  poison  suffi- 
cient to  destroy  life  was  found  in  the  dead  body,  the  chemical  evidence 
of  poisoning  was  defective.  But  it  is  now  a  well-known  fact  that 
a  person  may  die  from  the  effects  of  a  large  dose,  and  very  little  or 
even  not  a  trace  of  the  noxious  agent  remain  in  the  body  at  the  time 
of  death.  As  any  of  the  poison  remaining  in  its  free  state  in  the 
stomach  at  the  time  of  death  had  no  part  in  producing  the  fatal 
result,  it  is  obvious  that  to  recover  a  fatal  quantity  from  that  which 
had  been  absorbed,  and  which  was  really  the  cause  of  death,  even 
granting  that  none  had  been  eliminated  from  the  body  with  the 
excretions,  would  require  an  analysis  of  the  entire  body  and  the 
recovery  of  every  portion  of  the  poison  from  the  complex  mass, — 
the  first  of  which  is  impracticable  and  the  second  impossible.  It  is 
only,  therefore,  in  cases  in  which  more  than  a  fatal  dose  remains  in 
the  body  at  death  that  we  are  able  to  recover  sufficient  to  destroy 
life.  Moreover,  as  already  stated,  the  amount  of  poison  in  the  body 
at  the  time  of  death  is  in  itself  no  index  whatever  of  the  actual 
quantity  taken. 

Value  of  individual  chemical  Tests. — The  result  of  a  chemical 
examination  will  depend,  at  least  in  great  measure,  upon  how  far  we 
are  acquainted  with  reactions  peculiar  to  the  substance  under  consid- 
eration ;  the  delicacy  of  these  reactions ;  and,  in  many  instances,  our 
ability  to  separate  the  substance  from  foreign  matter.  There  is 
usually  no  difficulty  in  recognizing  the  presence  of  any  of  the 
mineral  poisons,  even  when  present  only  in  minute  quantity;  but  the 
case  is  very  different  in  regard  to  the  detection  of  many  of  the  organic 
poisons.  For  the  recognition  of  many  poisons  we  are  at  present 
familiar  with  several  tests,  the  reaction  of  each  of  which  is  charac- 
teristic of  the  substance;  while  for  the  detection  of  others  we  are 
acquainted  with  only  one  such  reaction ;  there  are  others  still  for 
which  we  have  no  specific  reagent,  but  whose  presence  can  be  fully 
established  by  the  concurrent  result  of  several  tests;  lastly,  there 
are  some  organic  poisons  for  the  detection  of  which,  at  present,  there 
is  not  known  even  any  combination  of  chemical  reactions  by  which 
their  presence  can  be  determined.  Some  of  the  poisons  of  the  last- 
mentioned  class  may,  in  the  form  of  leaves,  seeds,  or  roots,  be  rec- 
ognized by  their  botanical  characters ;  and  others,  by  their  peculiar 


VALUK   OF   CHEMICAL   ANALYSIS.  51 

physioloj^ieal  effects,  especiiiUy  when  llicse  are  (akcii  in  connection 
with  some  of  their  ooncral  chcMuical  in-opcrties.  Anionj^  the  poisons 
that  can  he  readily  dek-ctcd  when  in  (heii-  pure  state,  tliei-e  are  some 
which  when  present,  even  in  (pntc  notalih;  (|iianlit\',  in  complex 
organic  mixtures,  adhere  so  (cnaciously  to  the  foreij^n  or<i,ani('  matter 
that  it  is  dillicult  or  impossible  to  separate  them  in  astate  sulliciently 
pure  to  determine  their  presence. 

For  the  detection  of  all  the  poisons  considered  in  the  present 
volume,  with  the  exception  of  aconitine,  we  are  acquainted,  under 
certain  conditions,  with  one  or  more  special  chemical  reactions;  and 
most  of  them,  especially  by  the  aid  of  the  microscope,  can  now  be 
recoonized  with  absolute  certainty,  and  separated  from  complex 
organic  mixtures,  even  when  present  only  in  exceedingly  minute 
quantity.  Thus,  at  present  we  can  recognize  by  chemical  means, 
when  in  its  pure  state,  the  presence  of  the  1-1 0,000th  of  a  grain, 
and  in  some  instances  even  less,  of  either  arsenic,  mercury,  strych- 
uine,  or  hydrocyanic  acid,  with  absolute  certainty.  It  does  not,  how- 
ever, follow  that  quantities  as  small  as  these  when  present  in  complex 
mixtures  can  be  recovered  and  their  nature  then  established.  It  is  a 
popular  idea,  and  indeed  a  very  fair  inference  from  the  statements  of 
some  writers,  that  the  quantity  of  a  substance  that  can  be  recognized 
by  chemical  means  in  its  pure  state  represents  that  which  can  be 
detected  under  all  circumstances.  But  this  is  a  great  error,  since  the 
quantity  that  can  thus  be  recognized,  and  the  amount  necessary  to  be 
present  in  a  complex  mixture  to  enable  us  to  separate  that  quantity, 
may  differ  many  hundreds  and  even  thousands  of  times :  the  dif- 
ference usually  being  in  proportion  to  the  complexity  of  the  mixture. 

From  what  has  already  been  stated,  it  is  obvious  that  in  determin- 
ing the  nature  of  a  suspected  substance  it  is  not  enough  that  it  yields 
affirmative  reactions  with  a  given  number  of  reagents ;  but  we  must 
know  that  one  or  more  of  these  taken  singly,  or  two  or  more  of  them 
taken  in  connection,  are  peculiar  to  the  substance.  Thus,  aconitine 
can  be  precipitated  by  several  different  reagents,  yet  none  of  these 
reactions  taken  singly  nor  several  of  them  taken  in  connection,  when 
obtained  from  small  quantities  of  organic  mixtures,  will  fully  estab- 
lish the  presence  of  this  alkaloid,  since  there  are  many  other  organic 
substances  which  yield  similar  results.  We  have,  however,  for  the 
detection  of  this  poison,  a  delicate  and  characteristic  test  in  its  pecu- 
liar physiological  eflPects.    Again,  morphine  yields  certain  results  with 


52  INTEODUCTION. 

several  diflFerent  reagents,  yet  neither  of  these  taken  singly,  when 
obtained  from  small  quantities  of  amorphous  organic  mixtures,  is 
characteristic  of  this  poison;  but  the  concurrent  action  of  two  or 
more  of  them  may  fully  establish  its  presence,  since  there  is  no  other 
substance  known  that  possesses  these  several  properties  in  commom 
with  morphine.  When,  however,  we  have  even  only  a  very  minute 
quantity  of  this  poison  in  its  crystalline  state,  then  one  or  more  of 
these  tests  taken  singly  may  be  characteristic,  since  most  of  the  fal- 
lacious substances  are  uncrystallizable.  It  frequently  happens  that 
a  test  of  this  kind  is  applied  under  conditions  in  which  the  substance 
having  reactions  similar  to  that  of  the  suspected  substance  could  not 
be  present,  when,  of  course,  an  affirmative  reaction  is  specific. 

The  true  nature  of  a  reaction  that  is  common  to  several  substances 
can  in  some  instances  be  readily  determined  by  means  of  the  micro- 
scope. Thus,  a  solution  of  silver  nitrate,  when  exposed  separately 
to  several  different  vapors,  becomes  covered  with  a  white  film ;  but 
hydrocyanic  acid  is  the  only  one  in  the  action  of  which  the  film  is 
Grystalline,  and  this  is  characteristic  even  with  the  reaction  of  the 
l-100,000th  of  a  grain  of  the  acid.  A  substance  may  yield  a  pecu- 
liar crystalline  precipitate  at  one  degree  of  dilution,  while  at  another 
the  precipitate  may  not  be  characteristic,  as  illustrated  in  the  action 
of  bromine  with  atropine,  which  yields  from  one  grain  of  a 
1— 20,000th  or  stronger  pure  solution  a  specific  crystalline  deposit, 
while  from  solutions  but  little  more  dilute  the  result  is  not  pe- 
culiar. 

So,  also,  the  true  nature  of  a  reaction  may  in  some  instances  be 
determined  by  submitting  the  result  to  a  subsequent  test.  A  slip  of 
clean  copper,  when  boiled  in  a  hydrochloric  acid  solution  of  either 
arsenic,  mercury,  antimony,  or  of  several  other  metals,  becomes 
coated  with  the  metal ;  but  when  the  coated  copper  is  heated  in  a 
reduction-tube,  arsenic  is  the  only  substance  that  will  yield  a  sub- 
limate of  octahedral  crystals,  and  mercury  the  only  one  that  will 
furnish  metallic  globules.  Some  tests  can  be  successfully  applied  only 
to  comparatively  pure  solutions,  whilst  others  can  be  thus  applied  to 
very  complex  mixtures.  The  copper  test  for  arsenic  and  mercury, 
just  mentioned,  yields  in  many  instances  much  the  same  results  in 
complex  mixtures  as  with  pure  solutions.  But  this  result  is  true 
only  in  regard  to  a  few  tests,  and  these  for  the  detection  of  mineral 
substances. 


VALUE   OF   CHEMICAL   ANALYSIS.  53 

In  examining;  a  suspected  substance  or  solution,  it  is  usually  l)est, 
especially  when  the  quantity  of  material  is  limited,  to  befz;in  with  the 
most  characteristic  test,  after  which,  if  it  produces  an  aflirmative  re- 
sult, one  or  more  corroborative  tests  should  be  employed.  In  many 
instances  the  j)ositive  reaction  of  a  single  test,  obtiiined  from  oven  a 
very  small  fractional  part  of  a  grain  of  the  poison,  may,  in  a  chemical 
point  of  view,  be  as  conclusive  of  its  presence  as  the  result  of  any 
number  of  tests  applied  to  any  quantity  of  the  substance  however 
great.  Yet,  for  medico-legal  })urposes,  it  is  always  best,  if  sufficient 
material  be  at  hand,  to  confirm  the  results  by  several  tests,  and,  when 
practicable,  show  the  presence  of  the  poison  by  two  or  more  inde- 
pendent methods. 

If  any  of  the  corroborative  tests  thus  applied  should  fail,  we  should 
be  able  to  account  for  the  failure.  This  may  be  due  to  want  of  deli- 
cacy on  the  part  of  the  reagent,  or  to  the  presence  of  some  substance, 
such  as  a  free  acid,  an  alkali,  or  other  foreign  matter,  which  prevents 
its  normal  action.  For  the  same  reason,  if  the  test  first  applied  should 
fail,  we  should  be  cautious  in  concluding  the  entire  absence  of  poison, 
unless  we  are  fully  acquainted  with  the  conditions  under  which  the  test 
was  applied.  Thus,  it  has  just  been  stated  that  copper  becomes  coated 
with  arsenic  when  heated  in  a  mixture  of  this  metal  and  hydrochloric 
acid,  but  we  may  have  an  impure  mixture  of  this  kind  in  which  the 
arsenic  will  not  be  deposited,  even  when  present  in  large  quantity. 
In  fact,  there  is  no  test  that  will  produce  with  a  given  substance  the 
same  results  under  all  conditions.  In  the  special  consideration  of  the 
individual  tests,  the  conditions  under  which  they  may  fail,  as  well 
as  the  fallacies  to  which  they  are  liable,  and  the  limit  of  each  for  pure 
solutions,  will,  as  far  as  practicable,  be  pointed  out. 

The  behavior  of  a  test  the  reaction  of  which  taken  alone  has 
no  positive  value,  is  often  important  in  directing  the  application  of 
other  tests.  A  solution  of  iodine  produces  a  distinct  reaction  even 
with  the  l-100,000th  of  a  grain  of  strychnine,  when  in  solution  in  one 
grain  of  water ;  yet,  as  this  reaction  is  common  to  most  of  the  alka- 
loids and  other  organic  substances,  the  mere  production  of  a  precipi- 
tate would  not  establish  the  presence  of  the  alkaloid  in  question. 
Should,  however,  this  test  under  proper  conditions  fail,  it  would  fol- 
low that  the  suspected  solution  did  not  contain  even  the  l-100,000th 
of  its  weight  of  the  alkaloid,  and  therefore  that  it  would  be  useless 
to  apply  any  less  delicate  test  for  this  poison  to  the  solution. 


54  INTRODUCTION. 

Failure  to  detect  a  poison. — Numerous  instances  are  reported  in 
which  persons  died  from  the  effects  of  poison  and  none  was  discovered 
by  chemical  analysis  in  the  body  after  death.  This  result  has  most 
frequently  been  observed  in  poisoning  with  organic  substances,  but 
it  has  happened  when  mineral  poisons,  and  even  those  which  are 
most  easily  detected  by  chemical  tests,  had  been  taken  in  large 
quantity. 

A  failure  of  this  kind  may  be  due  to  any  of  the  following  cir- 
cumstances :  1.  The  poison  may  have  been  one  of  the  organic  poisons 
which  cannot  at  present  be  recognized  by  chemical  tests.  2.  The 
quantity  present  in  the  part  examined  may  have  been  so  minute  as 
under  the  circumstances  not  to  admit  of  recovery,  or  at  least  in  a 
state  sufficiently  pure  to  permit  its  true  nature  to  be  established. 
3.  The  poison  may  have  been  removed  from  the  stomach  and  intes- 
tines by  vomiting  and  purging  or  by  absorption.  4.  The  absorbed 
poison  may  have  been  carried  out  of  the  system  with  the  excretions. 
6.  If  volatile,  like  hydrocyanic  acid  and  some  few  other  poisons,  it 
may  have  been  dissipated  in  the  form  of  vapor.  6.  It  may  have 
undergone  a  chemical  change  in  the  living  body,  or,  especially  if 
of  organic  origin,  have  been  decomposed  in  the  dead  body  if  far 
advanced  in  putrefaction. 

The  period  in  which  a  poison  may  be  entirely  expelled  from  the 
stomach  by  vomiting  is  subject  to  great  variation.  Dr.  Christison 
cites  two  instances  of  poisoning  by  arsenic  in  which  death  ensued 
under  much  vomiting  in  five  hours,  and  in  one  of  which  none  of  the 
poison  could  be  detected  either  in  the  contents  or  tissue  of  the  stomach, 
and  in  the  other  only  the  fifteenth  part  of  a  grain  was  recovered. 
In  two  other  instances  of  like  poisoning,  in  which  death  took  place 
in  eight  hours,  after  one  ounce  and  nearly  two  ounces  respectively 
had  been  taken,  not  a  trace  of  the  noxious  agent  was  discovered  in 
the  stomach.  On  the  other  hand,  Orfila  mentions  a  case  in  which 
arsenic  was  detected  in  the  contents  of  the  stomach  of  an  individual 
who  had  vomited  almost  incessantly  for  two  entire  days.  And  in  a 
case  which  we  examined  some  years  since,  in  which  there  had  been 
almost  incessant  vomiting  for  thirty -two  hours,  forty-two  grains  of 
arsenic  were  recovered  ;  it  having  been  taken  in  the  form  of  "  fly- 
powder,"  and  much  of  it  existing  in  the  solid  state  attached  to  the 
mucous  membrane  of  the  organ.  In  a  case  examined  by  Prof.  S.  A. 
Lattimore,  of  Rochester,  N.Y.,  one  hundred  and  three  grains  of 


VALUK    OF    CIIKMKJAL    ANALYSIS.  55 

arsenic  were  found  in  tlie  stomaoli  of  :i  wonuiii  who  died  iVoni  tlie 
effects  of  the  poison.  How  lon^;-  the  woman  survived  after  taking 
the  poison  in  tliis  case  is  not  known. 

Siniihir  results  hav(^  been  observed  in  regard  to  the  removal  of 
poison  from  the  stomach  and  bowels  by  absorption,  even  in  cases  in 
Avhich  there  was  neither  vomiting  nor  purging.  Comparatively  large 
quantities  of  some  of  the  organic  poisons  have  apparently  thus  dis- 
ap{)eared  within  a  very  few  hours.  In  a  case  of  poisoning  by  strych- 
nine, in  which  about  six  grains  had  been  taken  and  death  ensued  in 
six  hours,  repeated  analyses,  by  Dr.  Reese,  of  Philadelphia,  of  the 
contents  of  the  stomach  and  of  a  portion  of  the  small  intestines,  made 
eight  weeks  after  death,  failed  to  reveal  the  presence  of  a  trace  of 
the  poison.  So  also,  in  a  case  of  poisoning  by  not  less  than  two 
ounces  of  laudanum,  Dr.  Christison  failed  to  detect  morphine  in  the 
contents  of  the  stomach,  although  the  person  survived  the  taking  of 
the  poison  only  five  hours.  Some  of  the  mineral  poisons  may  remain 
in  the  contents  of  the  living  stomach  and  intestines  for  several  days. 
Thus,  Dr.  Geoghegan  found  arsenic  in  the  contents  of  the  colon  after 
twelve  days. 

After  a  poison  has  been  absorbed  and  carried  into  the  tissues  of 
the  body,  it  is  sooner  or  later  eliminated  from  the  body  with  the 
different  excretions,  more  especially  with  the  urine.  Many  instances 
are  recorded  in  which  death  took  place  with  the  usual  rapidity  from 
the  effects  of  large  doses  of  the  most  easily  detected  mineral  poisons, 
and  there  was  a  failure  to  discover  the  poison  in  any  part  of  the 
body.  Orfila  concluded  from  his  investigations  that  arsenic,  mer- 
cury, and  the  mineral  poisons  generally  were  under  ordinary  circum- 
stances entirely  eliminated  from  the  living  system  in  about  fifteen 
days,  and  this  view  has  been  sustained  by  the  observ^ations  of  others. 
The  period  of  entire  elimination,  however,  is  subject  to  considerable 
variation :  it  has  been  limited  to  a  few  days,  while,  on  the  other 
hand,  some  of  the  mineral  poisons  have  been  detected  in  the  urine 
even  several  weeks  after  they  were  taken  into  the  stomach.  Thus, 
arsenic  has  been  found  in  the  fseces  passed  two  weeks,  and  in  the 
urine  voided  six  weeks,  after  the  metal  had  been  taken,  and  copper 
has  been  present  in  the  liver  even  three  months  after  being,  adminis- 
tered in  divided  doses. 

There  is  no  lono-er  anv  doubt  whatever  that  the  vegetable 
poisons,  such  as  the  alkaloids,  enter  the  blood  by  absorption,  in  part 


56  INTRODUCTION. 

at  least,  in  their  unchanged  state,  and  are  thus  conveyed  to  the  tis- 
sues ;  but  there  has  not  unfrequently  been  a  failure  to  recover  them 
from  the  blood  and  tissues,  even  under  apparently  the  most  favorable 
circumstances.  We  have  recovered  all  the  poisons  of  this  class  con- 
sidered in  the  present  treatise  from  the  blood  of  poisoned  animals, 
but  that  they  should  always  be  recovered,  even  under  favorable  con- 
ditions, from  the  blood  of  the  poisoned  human  subject,  we  will  not 
pretend  to  assert ;  still,  with  improved  methods  of  analysis  and  the 
aid  of  the  microscoj^e,  there  is  little  doubt  that  failures  of  this  kind 
will  become  less  frequent. 

In  regard  to  the  effects  of  chemical  changes  and  decomposition  in 
removing  poison  beyond  the  reach  of  analysis,  it  may  be  remarked 
that  some  of  the  organic  poisons,  especially  when  of  a  volatile 
nature,  may  undergo  a  change  of  this  kind  in  the  dead  bodv  after 
very  short  periods.  In  a  case  of  suicide  by  hydrocyanic  acid, 
quoted  by  Professor  Casper,  no  trace  of  it  was  found  in  the  stomach 
twenty-sis  liours  after  death,  but  there  was  present  a  considerable 
quantity  of  formic  acid,  as  the  result  of  the  metamorjihosis  of  the 
original  poison.  In  like  manner,  hydrocyanic  acid  may  be  converted 
into  sulphocyanic  add  during  the  process  of  putrefaction.  So  also, 
phosphorus,  by  combining  with  oxygen,  is  sooner  or  later  converted 
into  one  or  more  of  the  acid  oxides  of  phosphorus ;  this  conversion 
may  even  be  completed  in  the  living  body.  It  need  hardly  be 
remarked  that  when  a  chemical  antidote  has  been  administered, 
none  of  the  poison  may  remain  in  its  uncombined  state,  or  in  the 
form  in  which  originally  taken,  in  the  stomach. 

On  the  other  hand,  some  of  the  vegetable  alkaloids  raay  remain 
in  their  unchanged  state  in  the  dead  body  and  other  decomposing 
organic  mixtures  for  at  least  some  months.  Although  the  metallic 
poisons  may  undergo  chemical  changes,  even  in  the  living  body,  yet, 
as  the  metals  themselves  are  indestructible,  the  compounds  thus  pro- 
duced may  in  some  instances  be  recovered  even  after  many  years. 

Of  chemical  reagents. — Only  those  having  practical  experience 
in  the  matter  know  the  difficulty  of  obtaining  at  least  certain  re- 
agents and  chemicals  in  a  state  of  absolute  purity.  The  impurity 
may  in  some  instances  be  an  ordinary  poison,  and  even  consist  of  the 
very  substance  suspected  to  be  present  in  the  matters  submitted  for 
examination  ;  while  in  others  it  may  be  of  a  nature  that  will  very 
much    modify   or  altogether    prevent    the    normal    reaction   of  the 


CJIEMUAL    KKAOENTS.  57 

reagent,  or  give  rise  to  results  which  may  readily  be  attrihiitod  to 
sonic  other  cause.  Thus,  in  one  of  the  methods  for  the  detection  of 
arsenic,  the  j)rincipal  chemicals  employed  are  sul})huric  acid  and 
zinc,  yet  arsenic  is  not  nii(Ve<jnently  present  as  an  impurity  in  each 
of  these  chemicals.  Iiiij)uiilics  of  this  kind  generally  consist  of  in- 
organic substances,  and  are  chiefly  confined  to  inorganic  reagents. 
Although,  under  ordinary  circumstances,  there  would  be  no  proba- 
bility of  a  reagent  containing  any  of  the  organic  poisons,  such  as 
strychnine,  morphine,  and  the  like,  still  an  impurity  of  a  reagent 
used  for  the  detection  of  any  of  these  poisons  might  lead  to  erro- 
neous conclusions. 

The  analyst  should  never  accept  any  reagent  or  chemical  as  pure 
until  he  has  fully  established  its  purity  for  himself;  and  if  there  be 
any  possibility  of  its  having  become  changed  since  last  examined, 
the  examination  should  be  repeated.  This  latter  precaution  is  neces- 
sary, since  reagents,  when  frequently  used  for  general  analyses,  are 
quite  liable  to  become  more  or  less  contaminated ;  and  some  reagents 
may  even  speedily  undergo  spontaneous  changes.  All  liquid  reagents 
should  be  preserved  in  hard  German-glass  bottles,  and  handled  only 
by  means  of  perfectly  clean  pipettes.  If  poured  from  the  mouth  of 
the  bottle,  it  is  difficult  to  control  the  amount  used ;  and,  moreover, 
the  portion  left  adhering  to  the  neck  of  the  bottle  may  by  the  action 
of  the  atmosphere  become  changed,  and  afterward  fall  back  into  the 
solution,  and  thus  contaminate  it.  It  need  hardly  be  added  that  no 
other  than  pure  distlUed  water  should  be  used  for  the  solution  of 
reagents,  and  in  all  chemical  operations. 

In  applying  a  reagent  to  a  suspected  solution,  it  should  be  borne 
in  mind  that  the  results  may  be  much  modified  by  the  quantity 
employed.  In  some  instances,  a  very  slight  excess  of  the  reagent  may 
entirely  prevent  the  formation  of  a  precipitate  which  would  other- 
wise take  place.  Thus,  a  solution  of  morphine,  when  treated  with 
a  given  quantity  of  potassium  hydrate,  may  yield  a  copious  crys- 
talline deposit,  while  with  slight  excess  of  the  reagent  it  may 
yield  no  precipitate  whatever.  On  the  other  hand,  a  deficiency  of 
reagent  may  produce  results  very  different  from  those  occasioned 
by  other  quantities.  A  limited  quantity  of  sulphuretted  hydrogen 
throws  down  from  a  solution  of  corrosive  sublimate  a  white  pre- 
cipitate; while  excess  of  the  reagent  produces  a  black  deposit.  Any 
quantity  of  a  reagent  above  that  necessary  to  produce  the  desired 


58  INTRODCrCTION^. 

result,  is  an  excess,  and  may  do  harm,  if  only  by  diluting  the 
mixture. 

All  apparatus  employed  in  contact  with  the  suspected  substance 
under  examination  should  either  be  of  glass  or  of  well-glazed  porce- 
lain, and  be  washed  with  scrupulous  care.  In  fine,  any  article  about 
to  be  thus  employed,  whose  purity  is  not  entirely  above  suspicion, 
should  be  rejected. 

Qualifieations  of  the  analyst. — A  chemico-legal  investigation  of 
this  nature,  as  well  remarked  by  Prof.  Otto  in  regard  to  the  detec- 
tion of  arsenic,  should  be  intrusted  only  to  an  experienced  chemist. 
He  should  not  only  be  acquainted  with  the  principles  involved  in 
the  analysis,  but  know  from  experience  how  to  perform  it  in  all  its 
details,  and  be  able  to  defend  his  conclusions  from  any  objections 
that  might  arise  at  a  subsequent  trial.  If  he  be  unacquainted  with 
the  details  of  the  analysis  of  the  special  poison  under  consideration, 
he  should  first  familiarize  himself  with  them  by  repeated  experiments 
upon  known  and  minute  quantities  of  the  substance  suspected  to  be 
present,  under  conditions  similar  to  those  under  which  it  is  supposed 
to  exist.  To  point  out  the  methods  by  which  the  presence  of  any  of 
the  poisons  herein  considered  may  be  fully  established,  and  to  give  di- 
rections whereby  those  having  only  a  limited  experience  in  this  branch 
of  chemistry  may  acquaint  themselves  with  the  details  of  the  analysis, 
are  among  the  objects  of  the  following  pages. 

In  the  special  consideration  of  the  different  poisons,  they  will  be 
grouped  together  in  accordance  with  their  chemical  relations  or  for 
convenience,  rather  than  in  regard  to  their  physiological  effects.  They 
will  be  discussed  under  two  general  Parts  of  the  work:  Part  First 
will  contain  the  inorganic  poisons,  with  which  will  be  included 
Hydrocyanic  and  Oxalic  acids ;  Part  Second  will  be  confined  to  the 
consideration  of  vegetable  poisons. 

As  an  Appendix  will  be  added  a  chapter  on  the  Nature,  the  various 
methods  of  Detection,  and  the  Microscopic  Discrimination  of  Blood. 


PART  FIEST. 


INORGANIC  POISONS. 


INORGANIC  POISONS. 


CHAPTER    I. 

THE  ALKALIES:    POTASH,  SODA,  AMMONIA. 

Geneeal  Chemical  Nature. — In  their  general  chemical 
nature  the  alkalies,  potash,  soda,  and  ammonia,  and  their  salts,  form 
a  quite  natural  and  distinct  group  of  compounds.*  "When  in  solu- 
tion, either  in  their  uncombined  state  or  as  normal  carbonates,  they 
have  a  strong  alkaline  reaction,  immediately  restoring  the  blue  color 
of  reddened  litmus-paper.  They  differ  from  most  other  metallic 
oxides  in  being  freely  soluble  in  water;  the  same  is  also  true  in 
regard  to  many  of  their  salts,  especially  their  sulphides  and  carbon- 
ates. From  their  aqueous  solutions  they  are  not  precipitated  under 
any  condition  by  either  sulphuretted  hydrogen,  ammonium  sulphide, 
or  sodium  carbonate ;  whereas  all  other  metals  are  precipitated  by 
one  or  more  of  these  reagents.  This  difference  of  behavior  is  due 
to  the  fact  that  the  sulphides  and  carbonates  of  the  alkalies  are 
freely  soluble,  whilst  the  corresponding  salts  of  all  other  metals  are 
insoluble  in  water.  I^or  do  the  alkalies  precipitate  each  other  when 
in  solution  in  their  free  state;  and  the  same  is  true,  with  very  few 
exceptions,  in  regard  to  their  salts.  As  potash  and  soda,  and  their 
salts,  unlike  ammonia  and  its  salts,  are  not  dissipated  upon  the 
application  of  heat,  they  are  called  fixed  alkalies. 

Physiological  Effects. — Although  the  alkalies  and  many  of  their 
salts  are  highly  poisonous,  yet  they  have  very  rarely  been  adminis- 
tered criminally  or  taken  for  the  purpose  of  suicide.     They  have, 

"*  In  the  present  consideration  of  the  distinguishing  properties  of  the  above- 
named  alkalies,  the  properties  of  the  compounds  of  the  very  rare  alkali-metals 
lithium,  csesium,  and  rubidium  will  be  entirely  excluded. 

61     * 


62  THE   ALKALIES. 

however,  not  unfrequently  been  taken  by  accident  and  produced  fatal 
results.  As  the  effects  of  the  different  alkalies  upon  the  animal 
economy  are  very  similar  in  their  nature,  they  will  in  this  respect  be 
considered  together ;  but  treated  of  separately  when  considering  their 
chemical  properties. 

Symptoms. — 1.  Of  the  fixed  Alkalies. — When  a  strong  solution 
of  either  of  these  compounds  or  of  their  carbonates  is  taken  into 
the  mouth,  the  individual  immediately  experiences  a  nauseous  acrid 
taste,  and  there  is  rapid  disorganization  of  the  mucous  membrane 
of  the  parts  with  which  it  comes  in  contact.  On  account  of  the 
immediate  and  exceedingly  acrid  taste  of  these  substances,  the  solu- 
tion is  sometimes  rejected  from  the  mouth  without  any  portion  of 
it  being  swallowed.  If  the  solution  be  swallowed,  it  gives  rise  to 
a  sense  of  burning  heat  and  constriction  in  the  fauces,  oesophagus, 
and  stomach,  followed  by  violent  vomiting  of  mucous  matters,  which 
sometimes  contain  blood.  These  symptoms  are  generally  followed 
by  intense  pain  in  the  stomach,  tenderness  of  the  abdomen,  bloody 
purging,  great  muscular  prostration,  and  sometimes  convulsions. 
The  pulse  becomes  rapid,  small,  and  thready ;  the  skin  covered  with 
cold  perspiration ;  and  the  mouth,  tongue,  and  throat  inflamed  and 
swollen.  If  the  patient  survive  a  few  days,  there  may  be  sloughing 
of  the  fauces,  which  may  end  in  stricture  of  the  oesophagus,  and 
thus  death  finally  take  place  from  starvation.  Death  has  in  some 
instances  resulted  from  inflammation  and  obstruction  of  the  air- 
passages. 

In  a  case  reported  by  Dr.  Ogle  [St.  George's  Hosp.  Reports,  iii. 
233),  a  woman  swallowed  a  quantity  of  an  impure  solution  of  caustic 
potash.  She  vomited  immediately,  and  soon  after  the  mouth  and 
fauces  were  found  much  corroded.  Great  pain  was  experienced  in 
the  region  of  the  stomach  and  the  course  of  the  diaphragm.  On 
the  third  day  vomiting  came  on,  and  there  was  some  dysphagia  and 
pain  at  the  top  of  the  sternum,  but  no  tenderness  or  pressure  at  the 
epigastrium.  After  several  days  the  mouth  and  fauces  were  abraded, 
and  later  there  was  great  tenderness  and  pain  at  the  stomach ;  the 
pulse  became  quickened,  the  tongue  shining  and  glazed.  Subse- 
quently nothing  could  be  retained  in  the  stomach,  and  the  woman 
died,  from  inanition,  something  over  two  months  after  the  caustic 
liquid  had  been  taken.  In  another  case  related  by  the  same  writer, 
the  taking  of  a  similar  solution  was  soon  followed  by  bloody  vomiting. 


PIIYSIOIOOTfAT-    EFFECTS.  63 

wliicli  continued  three  days;  death  ensued  after  some  weeks,  from 
exhaustion. 

2.  OJ  Ainu\o)xia. — The  effects  produced  by  strong  solutions  of  am- 
monia, as  common  aqua  avimoniw,  are  much  the  same  as  those  of 
the  fixed  alkalies  and  their  carbonates ;  but  in  some  instances  it  is 
even  more  severe  in  its  action.  With  very  few  exceptions,  instances 
of  poisoning  by  this  substance  have  been  the  result  of  accident;  and 
in  some  of  these  death  took  place  with  great  rapidity.  In  a  case  of 
poisoning  by  a  solution  of  this  kind  taken  with  suicidal  intent, 
quoted  by  Dr.  Stills,  the  symptoms  were  collapse,  serous  and  bloody 
purging,  bloody  vomiting,  excruciating  pain  in  the  abdomen,  and 
death  in  six  hours.  If  the  patient  survive  the  primary  effects  of 
this  poison,  he  is  less  likely  to  die  from  secondary  effects  than  in  poi- 
soning by  the  fixed  alkalies. 

In  a  case  related  by  Dr.  Stevenson  {Guy's  Hasp.  Reports,  xvii. 
225),  a  man  was  admitted  into  the  hospital  who  in  the  morning  had 
drunk  about  a  teaspoonful  of  strong  liquor  ammoniae  (sp.  gr.  .88). 
The  lips,  tongue,  tonsils,  and  uvula  were  much  swollen,  red,  and 
glazed,  with  here  and  there  flakes  of  white  epithelium  resting  upon 
the  surface.  There  was  some  impediment  to  breathing.  After  com- 
plaining of  slight  pain  in  the  abdomen,  the  patient  turned  over  on 
his  side,  became  blue  in  the  face,  and  expired  immediately,  without 
any  struggle  for  breath. 

Dr.  Garvin  reports  a  case  (Boston  Med.  and  Surg.  Jour.,  Aug. 
1880,  166)  in  which  a  man  was  given,  by  mistake,  four  tablespoon- 
fuls  of  aqua  ammoniae,  which  he  drank  rapidly,  not,  however,  quite 
draining  the  cup.  He  immediately  rejected  some  of  the  liquid  from 
the  mouth,  and  soon  afterward  vomited,  probably  discharging  a 
portion  from  the  stomach.  A  terrible  burning  sensation  of  the 
mouth  and  fauces  at  once  ensued ;  but  not  until  two  hours  after- 
ward did  he  complain  of  soreness  any  lower  down,  and  at  no  time 
did  that  become  a  marked  symptom.  After  about  three-quarters 
of  an  hour  some  vinegar  was  administered,  followed  by  demulcent 
drinks.  These  effects  were  followed  by  repeated  vomiting  of  bloody 
matters,  and  death  on  the  fifth  day  after  the  poison  had  been  taken. 

In  another  case  a  man  swallowed  with  suicidal  intent  eight  ounces 
of  liquor  ammoniae.  Four  hours  later,  when  admitted  to  the  hos- 
pital, he  was  semi-conscious,  the  pupils  were  widely  dilated,  the 
breathing  noisy  and  hurried,  the  pulse  very  rapid,  and  there  was  pro- 


64  THE    ALKALIES. 

fuse  sweating.  He  complained  of  great  pain  in  the  abdomen,  vom- 
ited a  quantity  of  blood,  mucus,  and  shreds  of  mucous  membrane. 
Six  hours  later,  he  was  very  hoarse  and  drowsy ;  his  face  dusky  and 
skin  dry.  Next  morning  his  lips  were  swollen,  tongue  dry,  and  the 
mucous  membrane  of  the  mouth  partly  eroded ;  the  fauces  were 
greatly  congested,  the  mucous  membrane  oedematous,  softened,  and 
inflamed.  There  was  great  pain  and  tenderness  in  the  abdomen  on 
the  slightest  pressure.  He  had  vomited  blood  twice  since  the  night, 
and  complained  of  burning  pain  in  the  throat  and  pit  of  the  stomach, 
and  there  was  incessant  retching.  He  died  thirty-six  hours  after 
swallowing  the  liquid,     {Medical  Times,  Feb.  1879,  241.) 

The  vapor  of  ammonia,  even  when  largely  diluted  with  atmos- 
pheric air  and  inhaled,  produces  violent  dyspncea,  severe  pain  in  the 
throat,  irritation  and  inflammation  of  the  air-passages  and  lungs, 
and  in  some  instances  death.  In  the  related  case  of  a  druggist,  who 
accidentally  inhaled  the  fumes  of  ammonia  from  a  broken  carboy, 
there  was  corrosion  of  the  mucous  membrane  of  the  mouth  and  nos- 
trils, great  difficulty  of  breathing,  feeble  and  irregular  pulse,  and  a 
bloody  discharge  from  the  mouth  and  nose.  These  effects  were  fol- 
lowed by  a  most  violent  attack  of  bronchitis,  during  which  the  pa- 
tient could  not  speak  for  several  days ;  but  he  ultimately  recovered. 
The  injudicious  use  of  this  vapor  for  the  purpose  of  rousing  persons 
from  a  state  of  insensibility  has  in  several  instances  been  followed 
by  fatal  results. 

The  carbonates  of  ammonium,  of  which  there  are  several,  are  less 
intense  in  their  action  than  a  solution  of  the  free  alkali,  their  in- 
tensity diminishing  in  proportion  to  the  increase  of  carbonic  acid 
present. 

Peinod  when  fatal. — In  poisoning  by  the  caustic  alkalies  or  their 
carbonates,  death  may  take  place  within  a  short  period  from  the  im- 
mediate effects  of  the  poison ;  or  the  patient  may  recover  from  the 
primary  irritation  and  ultimately  die  from  secondary  results  months 
or  even  years  after  the  substance  had  been  taken.  In  a  case  de- 
scribed by  Mr.  Dewar,  a  little  boy  who  swallowed  by  mistake  about 
three  ounces  of  a  strong  solution  of  carbonate  of  potassium,  died  from 
its  effects  in  twelve  hours  afterward.  {Edin.  Med.,  and  Surg.  Jour., 
XXX.  309.)  In  another  instance,  related  by  Dr.  Cox,  a  small  quan- 
tity of  deliquesced  carbonate  of  potassium  proved  fatal  in  twenty-four 
hours  to  a  child  aged  three  years. 


I>IIVSl(iI,()(;i('AI-    Kl'FKCrS.  65 

On  the  otliur  hiaul,  two  .sisters,  aj^ud  respectively  twelve  unci  six- 
teen years,  took  by  mistake  about  half  an  ounce  of  subcarbonate  of 
potassium  each.  Violent  symptoms  immediately  ensued,  and  in  the 
case  of  the  elder  continued  with  little  interruption  for  about  two 
months,  when  death  took  place.  In  the  case  of  the  other,  the  symp- 
toms abated  after  a  few  days;  but  they  again  returned,  and  finally 
proved  fatal  after  the  lapse  of  nearly  three  months.  {Beck's  Med. 
Jur.,  ii.  524.)  In  a  case  reported  by  Dr.  Deutscli,  a  solution  esti- 
mated to  contain  about  half  an  ounce  of  caustic  potash  did  not  prove 
fatal  until  after  a  period  of  twenty-eig-ht  weeks.  And  in  another, 
a  quantity  of  impure  carbonate  of  sodium  produced  stricture  of 
the  gullet,  of  which  the  patient  died  two  years  and  three  months 
after  having  taken  the  poison.  Sir  C.  Bell  relates  a  case  of  this 
kind,  in  which  death  did  not  take  place  until  after  the  lapse  of 
twenty  years. 

Solutions  of  ammonia  have  proved  rapidly  fatal.  In  a  case 
related  by  Pleuck,  a  quantity  of  liquor  amraoniffi  poured  into  the 
mouth  of  a  man  who  had  been  bitten  by  a  mad  dog  caused  death  in 
four  minutes.  {Christison  on  Poisons,  194.)  Dr.  Kern  relates  the 
case  of  a  man  of  intemperate  habits,  aged  seventy  years,  who  took 
two  swallows  of  spirits  of  ammonia;  he  was  immediately  afterward 
seized  with  a  seuse  of  suffocation,  cough,  and  vomiting,  and,  notwith- 
standing prompt  treatment,  he  died  within  fou7-  hours;  death  being 
preceded  by  delirium,  stupor,  and  spasms.  {Amer.  Jour.  Med.  Sci., 
Jan.  1870,  275.)  A  case  in  which  a  solution  of  ammonia  proved 
fatal  in  six  hours  has  already  been  cited.  In  a  case  reported  by  Dr. 
Fran9ais  {A^m.  d'Hi/g.,  1877,  i.  556),  ninety  grammes  (about  three 
ounces)  of  aqua  ammonise,  taken  by  a  young  woman,  did  not  prove 
fatal  until  the  eighth  day.  The  vapor  of  ammonia  applied  to  the 
nostrils  of  a  lad  laboring  under  a  fit  of  epilepsy  induced  bronchitis 
which  proved  fatal  in  forty-eight  hours.  In  a  somewhat  similar 
case,  death  ensued  on  the  third  day. 

Fatal  quantity. — It  is  impossible  at  present  to  state  with  any  degree 
of  certainty  the  smallest  quantity  of  either  of  the  substances  under 
consideration  that  might  prove  fatal.  In  most  instances  the  effects 
will  depend  rather  upon  the  degree  of  concentration  under  which  the 
substance  is  taken,  than  upon  the  absolute  quantity.  In  an  instance 
recorded  by  Dr.  Taylor  [op.  cit.,  328),  one  ounce  and  a  half  of  the 
common  solution  of  potash  of  the  shops  proved  fatal  to  an  adult  in 


66  THE   ALKALIES. 

seven  weeks.  The  quantity  of  the  caustic  alkali  taken  in  this  case 
did  not  perhaps  exceed  forty  grains,  which  is  the  smallest  fatal  dose 
we  find  recorded.  There  are  not  less  than  four  cases  reported,  two 
of  which  have  already  been  cited,  in  which  half  an  ounce  of  the  car- 
bonate of  potassium  proved  fatal :  in  all  of  these,  as  in  the  preceding 
case,  death  was  due  to  the  secondary  effects  of  the  poison. 

Solutions  of  ammonia  have  proved  fatal  when  taken  in  small 
quantity.  In  the  case  related  by  Dr.  Stevenson,  a  teaspoonful  of 
strong  liquor  aramonise  proved  rapidly  fatal  to  an  adult.  And  at 
least  two  fatal  instances  are  reported  in  each  of  which  not  over  two 
drachms  of  the  solution  had  been  taken. 

Instances  of  recovery  from  solutions  of  this  alkali  have  been  of 
more  frequent  occurrence  than  from  the  fixed  alkalies.  A  man  swal- 
lowed by  mistake  three  drachms  of  a  strong  solution  of  ammonia, 
and  as  much  of  the  sesquicarbonate,  dissolved  in  two  ounces  of  oil ; 
but  under  appropriate  treatment  he  recovered  in  about  eight  days. 
(Jlliarton  and  Stille's  Med.  Jur.,  502.)  Dr.  Blake  reports  a  case 
in  which  a  girl,  aged  fourteen  years,  swallowed  a  mixture  of  half  an 
ounce  of  aqua  ammonise  and  one  ounce  of  olive  oil,  and,  although  she 
lingered  in  great  agony  for  many  weeks  from  the  effects  of  the  mix- 
ture, she  eventually  recovered.  (St.  George's  Hosp.  Rep.,  1870,  75.) 
In  another  case,  a  boy,  aged  two  years,  took  half  an  ounce  of  very 
pungent  spirits  of  hartshorn,  and  recovered.  Instances  are  related 
in  which  recovery  took  place  even  after  more  than  an  ounce  of  the 
solution  had  been  taken.  In  a  case  reported  by  Dr.  Pellerin,  a  young 
woman  with  suicidal  intent  swallowed  at  a  draught  upwards  of  ten 
drachms  of  a  solution  of  ammonia.  Dr.  Pellerin  found  the  patient 
in  the  sitting  position,  having  on  her  knees  a  basin  containing  a  large 
quantity  of  stringy  salivary  fluid  with  a  few  streaks  of  blood.  The 
face  was  pale,  the  eyes  were  haggard  and  injected.  The  lips  pre- 
sented much  swelling,  and  also  redness,  which  extended  to  the  mouth 
and  fauces.  There  was  complete  aphonia ;  pain  in  the  pharynx  and 
epigastrium  ;  the  pulse  was  slow,  the  limbs  cold.  The  loss  of  voice 
lasted  three  days,  and  deglutition  was  almost  impossible.  Under 
active  treatment  the  woman  was  convalescent  in  a  week.  {Ifedico- 
Chir.  Rev.,  April,  1857,  500.) 

Teeatment. — The  antidote  for  poisoning  by  any  of  the  fi'ee 
alkalies  or  their  carbonates,  is  the  speedy  administration  of  a  solution 
of  some  of  the  mild  vegetable  acids, — such  as  acetic  acid  in  the  form 


POST-MORTEM    APPEAKANCES.  67 

of  diluted  viiioo:ar,  or  the  juiee  of  any  of  the  acid  fruits, — by  which 
the  j)oison  will  to  a  certain  extent  be  neutrali/x'd.  Large  quantities 
of  olive  oil  iiave  in  some  instances  been  administered  with  advantage. 
This  substance  may  convert  the  alkali  into  a  soap,  and  thus  prevent 
its  caustic  action.  Lar2:e  draughts  of  milk  may  also  be  used  with 
benefit.  In  poisoning  by  the  vaj)or  of  ammonia,  Dr.  Pereira  recom- 
mends the  inhalation  of  the  vapor  of  acetic  or  of  dilute  hvdrochioric 
acid. 

Post-mortem  Appearances. — These  will  depend  in  a  great 
measure  upon  the  length  of  time  the  patient  survived  the  taking  of 
the  poison.  In  acute  cases,  the  mucous  membrane  of  the  parts  with 
which  the  substance  comes  in  contact  is  more  or  less  disorganized, 
being  inflamed  and  broken  up  in  patches;  sometimes  there  is  ex- 
travasation of  disorganized  blood  upon  the  walls  of  the  organs  thus 
affected,  which  causes  them  to  present  a  bluish  or  black  appearance. 
This  appearance  is  sometimes  well  marked  in  the  mouth.  In  some 
instances,  large  portions  of  the  mucous  membrane  of  the  mouth, 
oesophagus,  and  stomach  are  entirely  removed. 

In  Mr.  Dewar's  case,  in  which  death  was  produced  in  twelve 
hours  by  a  solution  of  carbonate  of  potassium,  the  appearances  were 
much  the  same  as  those  just  described.  Thus,  the  mucous  membrane 
of  the  pharynx  and  oesophagus  was  almost  entirely  destroyed,  and 
dark  blood  extravasated  beneath  the  pulpy  mass;  in  the  stomach, 
the  mucous  membrane  was  destroyed  in  two  places,  and  these  patches 
covered  with  clotted  blood.  Similar  appearances  were  found  in  the 
case  that  proved  fatal  in  twenty-four  hours. 

In  the  case  related  by  Dr.  Ogle,  in  which  a  quantity  of  caustic 
potash  proved  fatal  after  about  two  months,  the  organs  of  the  thorax, 
the  tongue,  fauces,  and  pharynx  were  found  natural ;  but  at  the  upper 
part  of  the  oesophagus  three  distinct  cicatrized  bands  were  observed, 
contracting  the  mucous  membrane ;  the  lower  part  of  the  tube  was 
much  contracted,  its  lining  membrane  quite  destroyed,  and  the  muscu- 
lar coat  exposed.  The  external  tissues  of  the  oasophagus  were  much 
thickened,  and  the  tube  was  strongly  adherent  to  all  the  neighboring 
parts.  The  cardiac  orifice  of  the  stomach  was  so  contracted  as  barely 
to  admit  the  passage  of  a  director ;  the  mucous  membrane  at  the 
pyloric  end  of  the  organ  presented  a  large  and  dense  cicatrix,  which 
so  involved  the  adjacent  parts  as  to  obstruct  all  communication 
with  the  duodenum,  except  by  a  small  orifice  which  only  admitted 


68  THE   ALKALIES. 

an  ordinary-sized  probe.  The  other  portions  of  the  stomach,  and 
the  remainder  of  the  intestinal  tube,  as  also  all  the  other  abdominal 
organs,  were  healthy.  In  a  case  in  which  death  was  caused  by  the 
taking  of  a  solution  of  caustic  potash  four  months  previously,  there 
was  found  a  stricture  of  the  oesophagus  four  or  five  inches  in  extent, 
rendering  swallowing  impossible.  (Chem.  News,  Oct.  1867,  197.) 
In  Dr.  Deutsch's  case,  already  cited,  the  mucous  membrane  of  the 
lower  portion  of  the  oesophagus  was  found  so  greatly  thickened  that 
the  ojDening  into  the  stomach  was  nearly  obliterated. 

In  Dr.  Kern's  case,  in  which  a  solution  of  ammonia  proved  fatal 
in  four  hours,  the  mouth  and  throat  were  found  denuded  of  epithelium, 
and  inflamed ;  the  stomach  contained  a  bloody  fluid  having  the  odor 
of  ammonia;  at  its  lower  portion  the  epithelium  of  the  stomach  was 
destroyed,  and  the  muscular  coat  changed  into  a  black  pulpy  sub- 
stance. The  duodenum  and  the  serous  coat  of  the  stomach  nearest 
the  bowel  were  inflamed.  The  blood  remained  of  a  thin  fluid  con- 
sistence. In  the  case  in  which  a  teaspoonful  of  liquor  ammonise 
proved  rapidly  fatal,  related  by  Dr.  Stevenson,  the  mucous  membrane 
of  the  mouth  and  pharynx  was  found  red  and  glazed.  The  oesopha- 
gus was  intensely  red  throughout,  more  especially  at  its  lower  part, 
which  was  of  a  dark-purple  color ;  this  color  ceased  abruptly  at  the 
stomach.  The  upper  portion  of  the  oesophageal  mucous  membrane 
was  shreddy  in  a  longitudinal  direction.  The  epiglottis  was  slightly 
oedematous ;  the  loose  tissue  about  the  larynx  much  so.  The  mucous 
membrane  of  the  trachea  and  bronchi  was  thickened  and  injected. 
Both  lungs  were  gorged  with  blood  and  oedematous.  A  circular 
patch  of  the  gastric  mucous  membrane,  about  four  inches  in  diameter, 
was  injected,  and  the  membrane  here  was  thin ;  elsewhere  it  was 
thick,  pale,  and  coated  with  slimy  mucus.  Both  sides  of  the  heart 
contained  dark  fluid  blood. 

In  the  case  in  which  eight  ounces  of  liquor  ammonise  had  been 
taken,  there  were  signs  of  inflammation  all  along  the  digestive  tract. 
The  mucous  membrane  of  the  stomach  was  charred  and  destroyed, 
and  there  was  great  congestion  as  far  as  the  lower  end  of  the  jejunum. 
The  stomach  contained  about  ten  ounces  of  dark  altered  blood.  In 
another  case,  fatal  in  three  days,  the  lining  membrane  of  the  trachea 
and  bronchi  was  softened  and  covered  with  layers  of  false  membrane ; 
while  the  larger  bronchial  tubes  were  completely  obstructed  by  casts 
of  this  membrane.     The  mucous  membrane  of  the  gullet  was  soft- 


NITRATE   OP   POTASSIUM.  69 

ened,  aud  the  lower  ei)(l  oi"  the  tube  completely  destroyed.  The  an- 
terior wall  of  the  stomach  contained  an  aperture  about  an  inch  and 
a  half  in  diameter,  through  which  the  contents  of  the  organ  had 
escaped. 

In  chronic  cases,  the  lower  portion  of  the  o'sophagus  and  the 
stomach  are  frequently  much  contracted.  The  walls  of  the  stomach 
are  often  thickened,  and  the  lining  membrane  wholly  destroyed.  An 
ulcerated  and  o;angrenous  state  of  the  mucous  membrane  of  the 
stomach  and  intestines  has  also  been  observed.  And  in  sonie  in- 
stances other  of  the  abdominal  organs  have  been  much  disorganized. 

XiTRATE  OF  Potassium. — This  salt,  commonly  known  by  the 
name  of  saltpetre  or  nitre,  has  in  several  instances  been  taken  by 
accident,  with  fatal  results.  To  produce  serious  effects,  however,  it 
requires  to  be  taken  in  large  quantity,  such  as  half  an  ounce  or 
more.  The  symptoms  usually  observed  are  severe  burning  pain 
in  the  stomach  and  abdomen,  nausea,  vomiting  and  purging,  fol- 
lowed by  coldness  of  the  extremities,  tremors,  and  collapse.  The 
effects  of  large  doses  have,  however,  been  subject  to  considerable 
variation. 

In  a  case  recorded  by  Dr.  Beck,  a  dose  of  this  salt  taken  in  mistake 
for  Glauber's  salt,  proved  fatal  to  an  aged  man  m  half  an  hour; 
and  in  an  instance  cited  by  Orfila,  one  ounce  caused  death  in  three 
hours.  A  man  who  took  three  ounces  and  a  half  of  the  salt  at  a 
dose,  apparently  suffered  but  little  for  five  hours,  when  he  suddenly 
fell  out  of  his  chair  and  expired.  In  a  more  recent  case,  about  an 
ounce  of  the  salt  caused  the  death  of  a  strong  young  man  in  six 
hours.  When  first  seen  by  a  physician,  a  few  hours  after  taking  the 
dose,  the  patient  was  lying  on  his  back,  completely  insensible,  the 
skin  cold,  clammy,  and  blue;  pulse  irregular,  almost  imperceptible; 
from  time  to  time  there  were  sudden  contractions  of  the  pectoral 
muscles,  which  continued  for  some  seconds;  the  eyes  were  fixed, 
pupils  greatly  contracted  and  immovable.  {Jour,  de  Chim.  Med.,  Dec. 
1873,  542.)  Recovery  has  in  several  instances  taken  place  even 
after  so  much  as  two  ounces  of  the  salt  had  been  taken. 

The  treatment  consists  in  the  speedy  removal  of  the  poison  from 
the  stomach,  aud  the  subsequent  exhibition  of  demulcents.  No 
chemical  antidote  is  known. 

After  death,  the  stomach  has  been  found  highly  inflamed,  mottled 


70  THE    ALKALIES. 

with  dark-colored  patches,  and  the  mucous  membrane  partially  de- 
tached. Similar  appearances  have  also  been  observed  in  the  small 
intestines.  In  at  least  one  instance,  the  coats  of  the  stomach  were 
perforated  by  a  small  opening. 

In  the  case  fatal  in  six  hours,  mentioned  above,  all  the  signs  of 
asphyxia  were  found  :  thick  black  blood  filled  the  right  heart,  and 
there  was  great  congestion  of  the  lungs.  The  bronchial  ramifica- 
tions were  filled  with  froth  ;  their  mucous  membrane  was  normal, 
as  also  that  of  the  alimentary  canal.  The  liver,  spleen,  and  kidneys 
presented  nothing  abnormal ;  the  brain  was  healthy,  but  the  sinuses 
were  gorged  with  thick  black  blood.  Analyses  of  the  blood  and 
urine  showed  the  presence  of  a  potassium  salt. 

Chlorate  of  Potassium. — Although  usually  regarded  as  non- 
poisonous,  this  salt  has  of  late  years  caused  death  in  a  number  of  in- 
stances. In  one  of  these,  an  elderly  man  took  in  mistake  for  Epsom 
salt  something  over  an  ounce  fthirty-five  grammes)  of  potassium 
chlorate.  Death,  which  followed  in  seven  hours  after  the  ingestion 
of  the  salt,  was  preceded  by  the  following  symptoms :  vomiting, 
colic,  and  diarrhoea,  general  weakness  and  rigidity  of  the  limbs. 
After  death  the  skin  of  the  dorsal  and  lumbar  regions  presented  a 
slate-colored  appearance.  [Med.  Times,  Jan.  1881,  287.)  In  a  case 
related  by  Dr.  Kennedy  {Amer.  Jour.  Pharm.,  1878,  112),  about  half 
an  ounce  of  the  salt  proved  fatal  in  seven  hours,  under  vomiting, 
purging,  and  stupor,  to  a  child  aged  two  and  a  half  years. 

M.  Marchand  reports  a  series  of  cases  in  which  four  children,  from 
three  to  seven  years  of  age,  took  ten,  twelve,  and  twenty-five  grammes 
of  this  salt  in  less  than  a  day,  or  at  most  thirty -six  hours.  They  sud- 
denly vomited ;  the  urine  was  scanty  and  bloody,  the  skin  yellow ; 
there  was  rapid  emaciation  and  loss  of  strength ;  finally  cerebral 
symptoms,  delirium,  and  coma,  ending  in  death  in  three  instances. 
In  the  post-mortem  examinations  of  the  fatal  cases,  and  of  animals 
used  for  experiment,  the  most  characteristic  lesions  found  were  those 
of  the  blood  and  of  the  kidneys.  The  blood  presented  a  peculiar 
brown  or  chocolate  color,  which  was  unchanged  on  exposure  to  the 
air.  The  kidneys  were  enlarged,  of  a  brown  color  on  the  surface, 
and,  under  the  microscope,  the  urinary  canaliculi  of  the  medullary 
substance  were  distended  with  brownish,  granular  cylinders,  proceed- 
ing evidently  from  the  disintegration  of  the  red  corpuscles ;  the  renal 


CHLORATE    OF    POTASSIUM.  71 

iiiHainmatory  action  was  of  secondary  importance.    Under  the  spec- 
troscope, the  blood  presented  the  spectrum  of  metha)moglol)in. 

The  poisonous  action  of  ])otassium  chlorate,  accordinj^  to  M. 
Marchand,  is  due  to  its  oxidizing  action  upon  the  haemoglobin  of  the 
blood,  by  which  the  corpuscles  acquire  a  great  tendency  to  aggluti- 
nate. Thus  modified,  the  corpuscles  accumulate  in  the  different 
organs,  but  more  especially  in  the  kidneys,  where  they  form  brownish 
conglomerate  masses.  Death  results  either  directly  from  tlie  change 
in  the  blood,  or  from  disturbance  of  the  renal  functions,  whereby 
uraemic  phenomena  are  produced.  {Annales  d'Hygi^e,  Nov.  1880, 
485.) 

Dr.  Satlow,  of  Leipsic,  reports  tlie  case  of  a  boy,  aged  fifteen 
years,  who  swallowed  a  solution  of  potassium  chlorate  containing 
from  twenty-five  to  thirty  grammes  of  the  salt.  Soon  after  drinking 
the  solution,  the  patient  was  seized  with  frequent  vomiting  of  dark 
green  masses  very  similar  to  thin  faecal  discharges.  Death  ensued  on 
the  fourth  day,  resulting  gradually  from  increased  weakness  of  the 
heart,  accompanied  by  dyspnoea  and  feelings  of  coldness  and  paraly- 
sis of  the  feet  progressively  extending  upwards.  On  inspection,  the 
blood  was  found  of  a  peculiar  brown  color,  the  density  of  syrup,  and 
the  red  corpuscles  especially  affected,  being  pale  and  glutinous,  and 
gathered  together  in  irregular  clumps.  A  large  quantity  of  reddish- 
brown  fragments,  supposed  to  be  haemoglobin,  had  been  passed  with 
the  urine  two  days  before  death.  (Boston  3Ied.  and  Surg.  Jour.,  Jan. 
1882,  81.) 

In  a  case  reported  by  Dr.  Ferris,  in  which  a  large  spoonful  of 
the  salt  proved  fatal  to  a  strong  man,  on  post-mortem  examination 
the  auricles  of  the  heart  were  found  distended  to  their  utmost  capacity 
by  dark  coagula,  homogeneous,  and  of  sufficient  tenacity  to  support 
their  own  weight  and  sustain  the  coat  of  the  cavities  from  which  they 
were  drawn.  The  large  vessels  communicating  with  the  cavities 
were  also  full  of  similar  coagula.  On  removal  of  the  heart,  but 
little  blood  flowed  from  any  of  the  severed  vessels.  {Medical  Record, 
1873,  482.) 

In  a  fatal  case  of  poisoning  by  potassium  chlorate,  M.  Ludwig 
examined  the  blood,  the  contents  of  the  stomach,  and  the  urine.  The 
urine  was  turbid,  acid  in  reaction,  and  contained  an  abundant  sedi- 
ment, composed  of  blood-globules  in  small  number,  and  large  granu- 
lar casts.     He  failed  to  find  the  salt  either  in  the  blood,  in  the  urine, 


72  THE    ALKALIES. 

or  in  the  contents  of  the  stomach.  (Boston  Med.  and  Surg.  Jour., 
Feb.  1882,  127.) 

Dr.  T.  Croft  relates  a  case  {Gaillard's  Med.  Jour.,  Julv,  1883,  15) 
in  which  a  young  woman,  directed  to  gargle  with  a  solution  of  potas- 
sium chlorate,  and  occasionally  swallow  a  little  of  the  solution,  used 
in  this  manner  nearly  half  a  pound  of  the  salt  within  a  few  days. 
Violent  symptoms  then  appeared,  followed  by  death  seven  days  later. 
At  first  there  was  violent  vomiting  and  diarrhoea.  This  was  soon 
followed  by  complete  constipation  and  stoppage  of  the  urinary  secre- 
tion, persistent  nausea,  and  general  cyanosis,  the  blueness  extending 
even  to  the  finger-nails  and  toe-nails.  After  death,  the  skin  became 
clear,  and  marble -like. 

In  a  case  reported  by  Dr.  Bohn  {Med.  Times,  May,  1884,  666), 
a  man  took  in  teaspoouful  doses  during  thirty-six  hours  about  two 
ounces  of  the  salt.  Symptoms  of  general  collapse  followed,  and 
there  was  complete  suppression  of  urine.  A  little  urine  drawn  from 
the  bladder  contained  blood-corpuscles  and  brownish  tube-casts,  and 
exhibited  the  spectrum  of  methsemoglobin.  Death  occurred  on  the 
third  day,  being  preceded  by  jaundice.  On  inspection,  the  spleen, 
liver,  and  kidneys  were  found  of  a  brown  color,  and  the  nriniferous 
tubules  were  filled  with  brownish  masses. 

The  Tartrate,  Sulphate,  and  Oxalate  of  Potassiujj: 
have  in  several  instances  destroyed  life.  The  noxious  effects  of  the 
last-mentioned  salt,  however,  chiefly  depend  upon  the  oxalic  acid 
which  it  contains. 

In  a  case  of  fatal  poisoning  by  common  alum,  or  sulphate  of  potas- 
sium and  aluminiurn,  in  which  a  man,  aged  fifty-seven  years,  swal- 
lowed with  some  cold  water,  in  mistake  for  Epsom  salt,  about  an 
ounce  of  the  calcined  salt,  the  following  symptoms  were  observed : 
at  first  a  sense  of  violent  constriction  in  the  mouth,  throat,  and 
stomach;  incessant  nausea,  followed  by  a  single  bloody  vomiting, 
without  any  purging;  extreme  depression,  great  agony ;  small,  quick 
pulse;  rapid  respiration,  repeated  syncope,  and  death  in  eight  hours. 
The  post-mortem  examination  revealed  a  yellow,  abraded  condition 
of  the  mouth,  pharynx,  and  oesophagus,  with  swelling  of  the  tongue 
and  uvula;  general  inflammation  of  the  peritoneum;  kidneys  much 
injected ;  bladder  empty ;  heart  dilated,  with  soft  clots  of  a  currant- 
jelly  color.     [Annales  d'Hygi^ne,  Jan.  1873,  192.) 


potassium  oxidk. — potash.  73 

Chemical  Properties  of  the  Ai.kai.irs. 

Distinguisking  propei'ties. — Solutions  of  the  caudic  alkalies  are 
distinguished  from  those  of  their  carbonates  hy  tiie  latter  efferves- 
cing, from  the  escajie  of  carbonic  acid  gas,  when  acted  upon  by  hydro- 
chloric or  any  of  the  strong  acids.  Sulphate  of  Magneshjm,  at 
ordinary  temperatures,  throws  down  from  solutions  of  the  normal 
carbonates  {protocarhonates)  of  i\\Q  fixed  alkalien  a  white  precipitate; 
whereas  with  the  acid  carbonates  [bicarbonates)  it  })roduces  no  pre- 
cipitate. This  reagent  fails  to  precipitate  solutions  of  either  of  the 
carbonates  of  ammonium. 

Nitrate  of  Silver  produces  in  solutions  of  the ^xecZ  caustic  al- 
kalies a  brown  precipitate,  which  is  insoluble  in  excess  of  the  alkali ; 
while  in  a  solution  of  ammonia  it  produces  a  somewhat  similar 
precipitate,  readily  soluble  in  excess  of  the  alkali :  when,  therefore, 
the  reagent  is  not  added  in  sufficient  quantity,  the  ammoniacal  so- 
lution fails  to  yield  a  precipitate.  Solutions  of  the  carbonates  of 
either  of  the  alkalies  yield  with  this  reagent  a  yellowish- white 
precipitate,  which  in  the  case  of  the  fixed  alkalies  is  insoluble  in 
excess  of  the  alkaline  salt,  while  that  from  either  of  the  carbonates 
of  ammonium  is  soluble  in  excess  of  the  alkaline  compound.  The 
precipitation  of  the  acid  carbonates  by  this  reagent  is  attended  with 
effervescence,  due  to  the  escape  of  carbonic  acid  gas,  but  this  result 
is  not  observed  in  the  case  of  the  normal  carbonates. 

Corrosive  Sublimate  throws  down  from  solutions  of  the  fixed 
alkalies  a  bright  yellow  precipitate,  which  is  insoluble  in  excess  of  the 
alkali;  from  the  normal  carbonates  a  reddish-brown  ;  but  in  solutions 
of  the  acid  carbonates  it  produces  no  precipitate.  With  ammonia 
and  its  carbonates  this  reagent  produces  a  tchite  precipitate,  which 
is  somewhat  soluble  in  excess  of  the  alkaline  solution,  especially  in 
the  presence  of  ammoniacal  salts. 

The  different  alkalies  will  now  be  separately  considered,  in  regard 
to  their  chemical  nature  and  reactions,  and  the  methods  by  which 
they  may  be  recovered  from  organic  mixtures. 

Section  I. — Potassium  Oxide. — Potash. 

General  Chemical  Nature. — Potassium  oxide,  known  also  as 
anhydrous  jJotash,  is  a  compound  of  the  elements  potassium  and  oxy- 
gen, KjO ;  in  combination  with  the  elements  of  water,  with  which  it 


74 


POTASSIUM   OXIDE. — POTASH. 


unites  with  great  energy,  it  forms  potassium  hydrate,  KHO ;  thus, 
K2O  +  H20  =  2KHO.  Potassium  hydrate,  known  also  as  hydrate 
of  potash,  potassa  fusa,  and  caustic  potash,  when  pure,  is  a  white, 
brittle  solid ;  as  usually  met  with  in  the  shops  in  the  form  of  little 
sticks,  it  has  sometimes  a  grayish  or  brownish  color,  due  to  the  pres- 
ence of  foreign  matter.  When  exposed  to  the  air,  it  deliquesces  and 
slowly  absorbs  carbonic  acid,  becoming  changed  into  the  carbonate 
of  potassium. 

Potassium  hydrate  dissolves,  with  the  evolution  of  heat,  in  about 
half  its  weight  of  water ;  it  is  about  equally  soluble  in  alcohol.  Its 
solubility  in  alcohol  enables  us  to  separate  it  from  many  of  its  salts, 
such  as  the  different  carbonates,  nitrate  and  sulphate,  which  are 
insoluble  in  this  liquid.  An  aqueous  solution  of  caustic  potash 
changes  an  infusion  of  violets  or  of  red  cabbage  to  green,  an  infusion 
of  turmeric  to  reddish-brown,  and  immediately  restores  the  blue  color 
of  reddened  litmus,  even,  according  to  Harting,  when  the  alkali  is 
dissolved  in  75,000  parts  by  weight  of  water.  A  saturated  aqueous 
solution  of  the  pure  caustic  alkali  has  a  density  of  about  2,  and 
contains  about  70  per  cent,  of  the  anhydrous  alkali. 

The  following  table,  by  Dalton,  indicates  approximately  the  per- 
centage of  anhydrous  potassium  oxide  (K2O)  in  solutions  of  the 
alkali  of  the  diflPerent  given  specific  gravities : 


STRENGTH    OF    AQUEOUS   SOLUTIONS    OF   POTASSIUM   OXIDE. 


>p.  Gr. 

1  78 

Percentage 
K2O. 

56.8 

51.2 

...  46  7 

Sp.  Gr. 
1.36 

Percentage 
K2O. 
29.4 

1  68 

1  33 

26.3 

1  60 

1.28 

23.4 

1  52 

42  9 

1.23 

19.5 

1  47 

39  6 

1.19 

16.2 

1  44 

36  8 

1.15 

13.0 

1  42 

...    .           34  4 

1.11 

9.5 

1.39 

32.4 

1.06 

4.7 

Caustic  potash,  in  its  action  upon  animal  tissues,  is  the  most  de- 
structive of  the  alkalies.  When  rubbed  between  the  fingers,  by  its 
chemical  action  on  the  skin,  it  imparts  a  soapy  feel.  It  forms  soluble 
compounds  with  many  of  the  constituents  of  the  animal  tissues ;  and 
it  may  dissolve  and  perforate  the  coats  of  the  stomach  even  more 
readily  than  the  mineral  acids. 

The  salts  of  potassium  are  colorless,  except  those  in  which  the 


SPECIAL   CHK\fICAT.   rROI'KRTIES.  75 

cotistitucnt  acid  is  colored;  and  tliey  generally  oryslallize  without 
water  of  crystallization,  in  wliich  tliey  diller  in  most  instances  from 
the  correspond in<^  salts  of  sodium.  With  very  few  exceptions,  they 
are  freely  soluble  in  water. 

Special  Chemical  Properties. — Potassiimi  compounds  when 
heated  upon  a  clean  platinum  wire,  in  the  reducing  l>low-pipe  flame, 
impart  a  violet  color  to  the  outer  flame.  This  reaction  may  be  entirely 
masked  by  the  presence  of  even  a  small  quantity  of  sodium,  which 
gives  a  strong  yellow  color  to  the  outer  flame.  In  like  manner,  an 
alcoholic  solution  of  the  alkali  or  of  any  of  its  salts  burns  with  a 
violet  flame ;  but  this  reaction  is  also  obscured  by  the  presence  of 
sodium  compounds. 

On  account  of  the  solubility  of  most  of  the  compounds  of  potas- 
sium, there  are  but  few  reagents  that  precipitate  it  from  solution,  and 
these  only  when  tlie  solution  is  comparatively  strong.  Before  apply- 
ing any  liquid  test  for  the  detection  of  potassium  oxide  or  either  of 
the  alkalies,  the  absence  of  metallic  oxides  other  than  those  of  the 
alkalies  should  be  established.  This  may  be  done  by  treating  a 
small  portion  of  the  solution,  acidulated  with  hydrochloric  acid,  with 
sulphuretted  hydrogen  ;  another,  and  neutral  portion,  with  sulphide  of 
ammonium;  and  a  third  portion,  with  carbonate  of  sodium:  when, 
if  these  reagents  fail  to  produce  a  precipitate,  it  follows  that  the 
metallic  oxides  mentioned  are  absent. 

In  applying  a  liquid  reagent,  a  drop  of  the  suspected  solu- 
tion may  be  placed  in  a  watch-glass,  and  a  small  portion  of  the 
reagent  added  by  means  of  a  pipette.  The  mixture  may  then  be 
examined  by  the  microscope.  If  there  be  no  immediate  precipi- 
tate, it  must  not  be  concluded  that  the  base  in  question  is  entirely 
absent;  but  the  mixture  should  be  allowed  to  stand,  even  in  some 
instances  for  some  hours,  before  deciding  the  entire  absence  of  the 
substance. 

In  the  following  examinations  of  the  behavior  and  limit  of  the 
different  tests  for  the  alkali  under  consideration,  solutions  of  potas- 
sium chloride  and  of  potassium  nitrate  were  chiefly  employed.  The 
vulgar  fractions  used  indicate  the  fractional  part  of  a  grain  of  anhy- 
drous potassium  oxide  under  the  form  of  the  salt  employed,  in  solu- 
tion in  one  grain  measure  of  pure  water ;  and  the  results,  unless 
otherwise  stated,  refer  to  the  behavior  of  one  grain  of  the  solution, 
treated  in  the  manner  above  described. 


76  POTASSIUM  OXIDE. — POTASH. 

1.  Chloride  of  Platinum. 

Platinic  chloride  throws  down  from  solutions  of  salts  of  potas- 
sium, when  not  too  dilute,  a  yellow  precipitate  of  the  double  chloride 
of  platinum  and  potassium,  2KC1 ;  PtCl^,  which,  either  immedi- 
ately or  after  a  very  little  time,  becomes  converted  into  beautiful 
octahedral  crystals.  Solutions  of  the  free  alkali  should  be  treated 
with  slight  excess  of  hydrochloric  acid,  before  the  addition  of  the 
reagent.  From  dilute  solutions,  the  presence  of  a  little  free  hydro- 
chloric acid,  or  of  strong  alcohol,  facilitates  the  formation  of  the 
precipitate. 

The  precipitate  is  soluble  in  about  one  hundred  and  eight  parts 
by  weight  of  pure  water  at  the  ordinary  temperature,  but  it  is  much 
more  freely  soluble  in  hot  water;  it  is  somewhat  less  soluble  in 
water  containing  a  trace  of  hydrochloric  acid,  and  almost  wholly  in- 
soluble in  absolute  alcohol.  One  part  by  weight  of  anhydrous  potas- 
sium oxide  or  its  equivalent  in  the  form  of  a  salt,  yields  5.2  parts  of 
the  double  salt. 

1.  Jq-  grain  of  potassium  oxide  in  the  form  of  potassium  chloride,  in 

solution  in  one  grain  of  water,  yields  with  the  reagent  an  im- 
mediate yellow  crystalline  precipitate,  which  very  soon  increases 
to  a  copious  deposit.  On  stirring  the  mixture  with  a  glass  rod, 
it  leaves  lines  of  crystals  where  the  rod  has  passed  over  the 
watch-glass. 

The  same  amount  of  potassium  oxide  in  the  form  of  nitrate, 
yields  about  the  same  results. 

2.  Y^  grain  as  chloride :  crystals  are  immediately  perceptible,  and 

soon  there  is  a  fine  crystalline  deposit,  which  under  the  micro- 
scope presents  the  appearance  represented  in  Plate  I.,  fig.  1. 
When  the  potassium  is  in  the  form  of  nitrate,  the  precipitate  is 
a  little  more  slow  in  forming,  and  does  not  become  quite  so 
abundant. 

grain  :  in  about  two  minutes  there  is  a  perceptible  precipitate, 
and  after  a  little  time  a  quite  good  crystalline  deposit.  If  the 
mixture  be  stirred,  it  yields  streaks  of  granules.  From  the 
nitrate  of  potassium,  the  precipitate  is  more  slow  to  form  and 
does  not  become  so  abundant,  the  crystals  being  confined  to  the 
border  of  tlie  mixture.  A  l-200th  solution  of  the  nitrate  yields 
only  about  the  same  results  as  a  l-250th  solution  of  the  chloride. 


1 

25  0 


SPECIAL    rilEMICAI.    PIKJPERTItiS.  77 

4.  ijJ^Q  grain  :  in  about  ten  minutes  crystals  appear  around  tlie  mar- 
gin of  the  mixture;  these  increase,  and  in  about  three-quarters 
of  an  liour  there  is  a  quite  satisfactory  deposit  scattered  through 
tlie  body  of  the  drop.  Stirring  the  mixture  does  not  seem  to 
lacilitate  the  formation  of  the  deposit.  The  forms  of  the  crys- 
tals are  much  the  same  as  illustrated  above. 

A  l-400th  solution  of  the  nitrate  yields  only  about  the  same 
reaction  as  a  l-500th  solution  of  the  chloride.     A  l-500th  ho- 
lution  of  the  nitrate,  however,  will  yield  a  perceptible  deposit 
after  standing  about  an  hour.     In  these  experiments,  concen- 
tration of  the  mixture  from  evaporation  was  guarded  against, 
perhaps,  however,  not  perfectly. 
Harting  placed  the  limit  of  this  test,  when  applied  to  a  solution 
of  the  nitrate,  at  one  part  of  potassium  oxide  in  205  parts  of  water. 
{Gmelins  Handbook,  iii.  15.)     Lassaigne   fixed    the    limit  for  sul- 
phate of  potassium  at  one  part  of  the  alkali  in  200  parts  of  water. 
{Jour.  Chim.  Med.,  8,  527.)     And  for  the  acetate,  Pettenkofer  placed 
the  limit  at  one  part  of  potassium  oxide  in  500  parts  of  water,  after 
standing  from  twelve  to  eighteen  hours;  but  he  states,  when  common 
salt  is  present,  the  reaction   is  limited  to  one  part  of  the  alkali  in 
100  parts  of  water,  or  even  less.     {Gmelin,  x.  276.)     Neither  of  these 
observers,  however,  states  the  quantity  of  solution  employed  in  the 
experiment. 

Fallacy. — Chloride  of  platinum  also  produces  a  similar  yellow 
crystalline  precipitate  in  solutions  of  salts  of  ammonium.  The  ab- 
sence of  these  salts  should,  therefore,  be  established  before  concluding 
that  the  precipitate  consists  of  the  potassium  compound.  This  may 
be  done  by  adding  some  hydrate  of  lime  or  caustic  potash  to  a  small 
portion  of  the  suspected  solution  and  heating  the  mixture,  when  if  it 
contain  an  ammoniacal  salt  the  odor  of  this  alkali  will  be  evolved. 
Or,  the  precipitate  produced  by  the  platinum  reagent  may  be  heated 
to  redness,  when  the  potassium  compound  will  leave  a  residue  of 
chloride  of  potassium  and  metallic  platinum,  which,  when  treated 
with  a  small  quantity  of  hot  water  and  the  filtered  liquid  acted  upon 
by  a  solution  of  nitrate  of  silver,  will  yield  a  white  precipitate  of 
chloride  of  silver,  due  to  the  presence  of  the  alkaline  chloride; 
whereas  the  ammonium  compound  will  leave  upon  ignition  a  residue 
of  only  metallic  platinum,  which,  of  course,  will  yield  no  precipi- 
tate with  nitrate  of  silver. 


78  POTASSIUM    OXIDE. — POTASH. 

2.  Tartaric  Acid,  and  Sodium  Tartrate. 

Tartaric  acid,  when  added  in  excess  to  somewhat  strong  solutions 
of  potassium  compounds,  produces  a  white  crystalline  precipitate 
of  acid  tartrate  of  potassium,  KH.CJiJJQ.  From  somewhat  dilute 
solutions  the  precipitate  is  slow  in  appearing ;  in  such  cases,  its  for- 
mation is  much  facilitated  by  agitation,  as  also  by  the  addition  of 
alcohol.  The  precipitate  is  soluble  in  the  mineral  acids,  and  free 
alkalies  and  their  carbonates;  if,  therefore,  either  of  these  substances 
be  present  in  excess,  the  formation  of  the  precipitate  will  be  en- 
tirely prevented.  The  precipitate  is  insoluble  in  free  tartaric  and 
acetic  acids. 

When  a  solution  of  a  potassium  salt  is  treated  with  free  tartaric 
acid,  it  is  obvious  that  the  acid  of  the  salt  is  set  free  :  thus,  KNOgH- 
HaC^HPe^  KHC4HPg  +  HNO3.  The  acid  thus  set  free  may  in  a 
measure  redissolve  the  potassium  tartrate  produced  by  the  reagent, 
especially  if  it  be  one  of  the  stronger  acids.  This  elimination  of  the 
acid  may  be  prevented  by  using  the  reagent  in  the  form  of  a  solution 
of  the  acid  tartrate  of  sodium  (NaHC4H406),  as  first  recommended 
by  Mr.  Plunkett.  {Chem.  Gaz.,  xvi.  217.)  Under  these  conditions, 
there  would  simply  be  an  interchange  of  the  metals,  the  sodium 
eliminated  from  the  tartaric  acid  combining  with  the  acid  radicle 
set  free  from  the  potassium  salt.  This  reagent  is  readily  prepared 
by  dividing  a  strong  solution  of  tartaric  acid  into  two  equal  parts, 
exactly  neutralizing  one  of  them  with  pure  carbonate  of  sodium,  and 
then  adding  the  other. 

In  the  following  investigations  a  very  strong  solution  of  free  tar- 
taric acid,  and  a  saturated  solution  of  the  acid  tartrate  of  sodium, 
were  employed  as  the  reagents. 

1.  _i_  grain  of  potassium  oxide  in  the  form  of  chloride  or  nitrate, 
yields  with  free  tartaric  acid  an  immediate  crystalline  precipi- 
tate, which  soon  increases  to  a  very  good  deposit.  The  tartrate 
of  sodium  produces  much  the  same  results,  except,  perhaps,  the 
precipitate  is  somewhat  more  copious  ;  the  general  forms  of  the 
crystals,  however,  are  quite  different.  The  neutral  tartrate  of 
sodium  produces  no  precipitate. 


1 


100 


grain :  crystals  immediately  begin  to  separate,  and  after  a 
little  time  there  is  a  good  crystalline  deposit.  Plate  I.,  fig.  2, 
represents  the  usual  forms  of  the  crystals  produced  by  free  tar- 


SPECIAL    CHEMICAL    PROPERTIES.  79 

taric  acid.  Acid  tartrate  of  sodiiuii  produces  a  somewhat  more 
abundant  precipitate. 

3.  Y^  grain  :    in  a  lew   moments  crystals  appear,  and    very  soon 

there  is  a  qnitc  satisfactory  deposit.  Witli  the  tartrate  of 
sodium  and  chloride  of  pottussium,  the  precij)itate  is  somewhat 
more  prompt  in  appearing.  Plate  I.,  fig.  3,  represents  the  forms 
of  crystals  usually  produced  by  the  sodium  reagent. 

4.  y^  grain  as  chloride:  within  a  few  minutes  granules  appear; 

these  soon  become  crystalline,  and  after  a  little  time  there  is  a 
quite  satisfactory  crystalline  and  granular  deposit.  From  the 
nitrate  of  potassium  the  precipitate  separates  much  more  slowly, 
and  is  chiefly  confined  to  the  border  of  the  mixture ;  under  the 
microscope,  however,  the  reaction  is  quite  satisfactory.  After 
standing  about  half  an  hour,  either  of  these  solutions  yields 
a  quite  good  deposit  of  crystals  having  the  forms  illustrated 
above.  When  acid  tartrate  of  sodium  is  employed  as  the  reagent, 
the  precipitate  is  much  more  prompt  in  appearing,  particularly 
from  a  solution  of  potassium  chloride. 

5.  -y-g-jj-  grain  as  chloride:  after  about  ten  minutes,  small  granules 

form  along  the  margin  of  the  mixture,  and  after  some  minutes 
more,  there  is  a  quite  distinct  granular  and  crystalline  deposit. 
With  the  sodium  reagent,  granules  and  crystals  appear  within 
about  four  minutes,  and  there  is  soon  a  very  satisfactory  de- 
posit. 

6.  YoVo  gi'^iii  of  the  chloride,  with  acid  tartrate  of  sodium :  in  about 

five  minutes,  crystals  are  just  perceptible;    and  in  about  ten 

minutes,  the  deposit  is  quite  distinct,  but  confined  to  the  border 

of  the  drop.     The  crystals  have  the  forms  illustrated  above, 

some  of  them  being  quite  large. 

From  the  above  statements  it  is  obvious  that  the  chloride  of 

potassium  is  the  most  favorable  form  of  the  alkali  for  the  application 

of  either  of  the  above  reagents.     Pettenkofer  placed  the  limit  of  the 

reaction  of  free  tartaric  acid,  for  solutions  of  the  acetate  of  potassium, 

at  one  part  of  the  anhydrous  alkali  in  from  700  to  800  parts  of 

water,  after  standing  from  twelve  to  eighteen  hours. 

Fallaey. — These  reagents  also  produce  similar  crystalline  pre- 
cipitates from  solutions  of  ammonia  and  its  salts.  The  absence  of 
this  alkali  may  be  established  in  the  manner  indicated  under  the 
preceding  test. 


80  POTASSIUM   OXIDE. — POTASH. 


3.  PicriG  Acid. 

A  strong  alcoholic  solution  of  Picric  or  Carbazotic  acid,  when 
added  in  excess  to  solutions  of  caustic  potash  and  of  potassium  salts, 
produces  a  yellow  precipitate  of  picrate  of  potassium,  KCgH2(N02)30, 
which  is  insoluble  in  excess  of  the  precipitant  and  in  alcohol.  The 
precipitate  contains  the  equivalent  of  17.66  per  cent,  of  anhydrous 
potassium  oxide. 

1.  gL  grain  of  potassium  oxide  in  the  form  of  chloride  or  nitrate, 

yields  an  immediate  amorphous  precipitate,  which  in  a  few 
moments  becomes  converted  into  a  mass  of  long,  regular,  yellow 
crystalline  needles,  some  of  which  extend  entirely  across  the 
drop  of  liquid. 

2.  Yoo  gi"9'i^  •  crystals  immediately  begin  to  form,  and  in  a  very 

little  time  the  drop  becomes  a  mass  of  very  long,  slender, 
yellow  needles,  Plate  I.,  fig.  4. 

3.  2^0"  graiii  '•  i^^  ^  few  moments,  crystals  begin  to  form,  and  after 

a  little  time,  a  very  good  deposit  of  long  needles. 

4.  g-^  grain :  much  the  same  results  as  in  3.     From  the  nitrate  of 

potassium  the  precipitate  is  not  so  prompt  to  form,  nor  is  it  as 
abundant  as  in  the  case  of  the  chloride. 

5.  YTo  gi'^iii  ill  the  form  of  chloride,  yields  after  a  little  time  a  per- 

fectly satisfactory  crystalline  deposit. 

6.  Y^Vo  gi^ain :  after  a  few  minutes,  crystalline  needles  appear  along 

the  margin  of  the  drop ;  after  about  fifteen  minutes,  the  deposit 

becomes   quite  satisfactory,  especially  when   examined    by  the 

microscope. 

In  applying  this  reagent  it  should   be  added   in  large  excess. 

Thus,  ten  grains  of  a  l-500th  solution  of  potassium  oxide,  when 

acted  upon  by  a  drop  or  two  of  the  reagent,  yield  no  precipitate,  at 

least  for  some  time ;  but  if  an  equal  volume  of  the  reagent  be  added, 

it  produces  a  precipitate  within  a  few  moments. 

Fallacies. — Picric  acid  also  throws  down  from  solutions  of  ammo- 
nia and  very  strong  solutions  of  caustic  soda  yellow  crystalline  pre- 
cipitates. The  microscope,  however,  will  readily  enable  us  to  distin- 
guish the  potassium  precipitate  by  its  crystalline  form  from  that  of 
either  of  these  substances.  (Compare  figs.  5  and  6,  Plate  I.)  The 
reagent  also  produces  yellow  precipitates,  some  of  which  are  crystal- 


SPECIAL    CHEMK  AI,    IMIOPERTIES.  81 

line,  with  many  organic  substances,  especially  the  vegetable  alkaloids. 
So,  also,  it  occasions  ])recipitates  with  certain  other  metals ;  but  the 
absence  of  these,  as  already  })oiiited  out,  should  he  estal)lishod  before 
apply iuii-  the  test. 

Ill  applyinu'  this  test  it  must  be  remembered  that  a  very  strong 
alcoholic  solution  of  the  reagent,  when  added  in  certain  projiortiou  to 
pure  water y  may  yield  a  yellow  crystalline  precipitate  of  free  picric 
acid.  The  forms  of  these  crystals,  however,  readily  distinguish  them 
from  the  potassium  compound.  In  a  l-500th  or  stronger  solution  of 
tiie  alUali,  this  distinction  is  very  apparent  to  the  naked  eye;  and  in 
more  dilute  solutions,  it  is  readily  established  by  the  microscope. 

Other  Reactions  of  Potassium  Compounds. — L.  de  Koninck 
has  recently  shown  that  if  a  solution  of  a  potassium  compound  be 
treated  with  excess  of  about  a  ten  per  cent,  solution  of  Sodium  Ni- 
trite containing  a  little  Cobaltous  Chloride  and  Acetic  Acid, 
the  potassium  is  precipitated  as  the  double  nitrite  of  j^otassium  and 
cobalt,  the  reaction  being  more  sensitive  than  that  of  platinic  chlo- 
ride.   {Zeit.f.  Anal  Chem.,  1881,  390.) 

We  find  that  a  drop  of  a  1— 100th  solution  of  potassium  oxide  in 
the  form  of  a  salt  yields  with  a  drop  of  this  reagent  an  immediate, 
bright  yellow,  granular  or  crystalline  precipitate.-  With  a  l-oOOth 
solution  the  precipitate  will  appear  in  a  very  little  time;  and  it  may 
be  obtained  after  a  time  from  even  a  1— 1000th  solution  of  tlie  alkali. 
The  precipitate  is  insoluble  in  hydrochloric  acid,  even  when  added  in 
large  excess  ;  it  is  also  insoluble  in  sulphuric  and  nitric  acids. 

This  test  is  simply  a  modification  of  the  well-known  reaction  for 
cobalt  by  potassium  nitrite.  The  composition  of  the  precipitate,  ac- 
cording to  Prof.  Sadtler,  is  GKNO^;  Co^GNOg  +  Aq.  The  reagent 
produces  a  similar,  but  less  sensitive,  reaction  with  salts  of  ammo- 
nium. The  reaction  is  not  interfered  with  by  the  presence  of  salts 
of  calcium,  magnesium,  iron,  aluminium,  or  of  zinc. 

Hydrofluosilicic  Acid  in  excess  produces  in  strong  solutions 
of  potassium  compounds  a  transparent  gelatinous  precipitate  of  the 
silicofluoride  of  potassium,  which  is  insoluble  in  hydrochloric  acid. 
In  concentrated  solutions  this  reaction  is  very  satisfactory.  A  1— 50th 
solution  of  the  alkali  in  the  form  of  chloride  yields,  after  a  time, 
only  a  slight  flocculent  deposit. 

Perchloric  Acid  produces  in  similar  solutions  a  white  erystal- 

6 


82  POTASSIUM   OXIDE. — POTASH. 

line  precipitate  of  potassium  perchlorate.  So,  also,  a  concentrated 
solution  of  Sulphate  of  Aluminium,  when  added  to  concentrated 
solutions  of  the  alkali  previously  acidulated  with  hydrochloric  acid, 
precipitates  crystals  of  the  double  sulphate  of  aluminium  and  potas- 
sium, or  common  alum  :  K2S04,Al23S04+24H20. 

As  a  delicate  reagent  for  the  precipitation  of  potassium  salts,  M. 
Carnot  recommends  to  dissolve  one  part  (0.5  gramme)  of  SuBNi- 
TEATE  OF  Bismuth  in  a  few  drops  of  hydrochloric  acid  ;  and,  on  the 
other  hand,  about  two  parts  (1  gramme)  of  crystallized  Hyposul- 
phite OF  Sodium  in  a  few  cubic  centimetres  of  water.  The  second 
solution  is  added  to  the  first,  and  then  strong  alcohol  added  in  large 
excess.  This  mixture,  or  reagent,  produces  in  solutions  of  potassium 
salts  a  yellow  precipitate  of  the  double  hyposulphite  of  bismuth  and 
potassium:  Bi^SSPsj  3KSA+2H2O.  {Chem.  News,  Sept.  1876, 
85,  120.)  This  reaction,  it  is  said,  is  not  interfered  with  by  the 
presence  of  other  bases. 

Spectrum  Analysis. — This,  as  first  applied  by  Professors  Kir- 
choff  and  Bunsen,  is  by  far  the  most  delicate  method  yet  discovered 
for  the  recognition  of  potassium, — as  well  as  of  sodium  and  many 
other  volatile  metals.  It  consists  in  introducing  a  small  portion  of 
the  caustic  alkali,  or  any  of  its  salts  containing  a  volatile  acid,  into 
the  flame  of  a  Bunsen  gas-burner  and  allowing  the  rays  of  the  col- 
ored flame  to  pass  through  a  prism.  The  refracted  rays  are  then 
examined  by  means  of  a  small  telescope,  when,  in  the  case  of  potas- 
sium, two  distinct  lines,  one  having  a  red  color  and  the  other  indigo- 
blue,  will  be  observed,  which  are  characteristic  of  this  metal.  The 
authors  of  this  method  estimated  that  it  would  reveal  the  reaction 
of  the  65,000th  part  of  a  grain  of  potassium,  and  the  195,000,000th 
part  of  a  grain  of  sodium.  (For  the  details  of  this  method,  see 
Quart.  Jour.  Chem.  Soc,  Oct.  1860;  also,  Fresenius's  Qualitative 
Analysis,  London,  1877.) 

Although  spectrum  analysis  has  very  largely  extended  the  scope 
of  chemical  research,  enabling  us  in  a  few  seconds  to  detect  the  pres- 
ence of  the  most  minute  traces  of  many  metals,  and  bringing  to  light 
substances  of  which  heretofore  we  had  no  knowledge ;  yet,  as  it  gives 
no  indication  whatever  as  to  the  quantity  of  the  substance  present,  it 
is  still  doubtful  whether  it  will  be  of  any  practical  value  in  chemico- 
legal  investigations,  at  least  for  the  detection  of  the  fixed  alkalies, 


SEPARATION    FKOM    OR(;ANIC    MIXTURES.  83 

since   thoi<o  aro  so  iii)ivei-s;illy  (listril)iUc<l   through   the  tissues  and 
juices  of  l)<)tli  animal  and  vegetable  structures. 

Separation  Fra)M  Okganic  Mixtures. 

^Mien  the  suspected  solution  is  highly  colored  or  contains  much 
orraiiic  matter,  the  tests  for  either  of  the  alkalies  cannot  be  satisfac- 
torily  applied  directly  to  the  mixture.  If  the  solution  has  a  soapy 
feel,  a  strong  alkaline  reaction,  and  is  destitute  of  the  odor  of  am- 
monia, even  when  a  small  portion  of  it  is  heated  with  hydrate  of 
lime,  the  presence  of  one  or  other,  or  both,  of  the  fixed  alkalies,  or 
of  their  carbonates,  may  bo  inferred. 

Either  of  the  fixed  alkalies  may  be  separated  from  their  carbonates 
and  organic  matter,  by  evaporating  the  mixture  on  a  water-bath  to 
about  dryness  and  digesting  the  cooled  residue  with  absolute  alcohol, 
which  will  dissolve  the  free  alkali,  while  its  carbonates,  and  other 
salts  if  present,  will  remain  undissolved.  The  alcoholic  solution  is 
then  concentrated  to  a  small  volume,  and,  if  strongly  alkaline  and 
nearly  colorless,  at  once  neutralized  with  hydrochloric  acid,  and  ex- 
amined by  the  appropriate  reagents.  If,  however,  it  contains  much 
organic  matter,  before  being  tested  it  should  be  evaporated  to  dry- 
ness, the  residue  incinerated  at  not  above  a  dull  red  heat  until  the 
organic  matter  is  entirely  destroyed,  and  the  cooled  mass  dissolved 
in  water;  the  aqueous  solution  is  then  examined  in  the  ordinary 
manner. 

Although  the  alkaline  carbonates  in  their  pure  state  are  almost 
wholly  insoluble  in  absolute  alcohol,  yet  the  presence  of  certain  kinds 
of  organic  matter  renders  them  slightly  soluble  in  this  menstruum. 
A  small  quantity  of  these  salts  may,  therefore,  be  extracted  along 
with  the  caustic  alkali  in  the  above  operation.  To  ascertain  the 
presence  of  fixed  alkaline  salts  in  the  residue  from  which  the  free 
alkali  was  extracted  by  alcohol,  the  mass  is  incinerated  in  the  manner 
directed  above,  and  the  cooled  residue  dissolved  in  distilled  water. 

Another  method  recommended  for  the  recovery  of  the  fixed  alka- 
lies and  their  carbonates  from  complex  organic  mixtures,  is  to  evapo- 
rate the  solution  to  dryness,  incinerate  the  dry  mass,  and  then  sepa- 
rate the  free  alkali  from  its  carbonate  by  means  of  absolute  alcohol. 
This  method  has  the  advantage  of  at  once  destroying  the  organic 
matter,  but  the  charring  of  this  converts  more  or  less  of  the  free 


84  SODA. 

alkali  into  carbonate,  the  quantity  thus  converted  depending  upon 
the  relative  amount  of  organic  matter  present.  The  amount  of  free 
alkali,  therefore,  furnished  by  this  method  would  be  somewhat  less 
than  originally  existed;  while  by  the  preceding  process  the  estimate 
of  this  substance  might  be  somewhat  too  high. 

Quantitative  Analysis. — The  quantity  of  caustic  jiotash  pres- 
ent in  pure  solutions  of  the  free  alkali  or  of  its  carbonates  may  be 
estimated  by  precipitating  it  in  the  form  of  the  double  chloride  of 
platinum  and  potassium.  For  this  purpose  the  alkali  is  converted 
into  chloride,  by  the  addition  of  hydrochloric  acid,  and  the  some- 
what concentrated  solution  treated  with  slight  excess  of  platinic  chlo- 
ride. When  the  jsrecipitate  has  completely  deposited,  the  mixture 
is  concentrated  on  a  water-bath  to  near  dryness,  and  the  cooled 
residue  washed  with  strong  alcohol,  which  will  remove  the  excess 
of  reagent  added.  The  residue,  consisting  of  the  double  salt,  is 
then  collected  on  a  filter  of  known  weight,  washed  with  a  little 
more  alcohol,  dried,  and  weighed.  Every  100  parts  by  weight 
of  the  double  salt  thus  obtained  represent  22.96  parts  of  caustic 
potash,  KHO ;  or  28.27  parts  of  anhydrous  carbonate  of  potassium, 
K2CO3. 

In  all  investigations  of  this  kind,  the  original  solution  presented 
for  examination  should  be  carefully  measured,  and  a  given  portion 
set  apart  for  the  quantitative  analysis.  From  the  amount  of  the 
alkali  discovered  in  this  the  entire  quantity  present  may,  of  course, 
be  readily  deduced. 

Section  II. — Soda. 

General  Chemical  Xature. — This  alkali,  in  the  form  of 
sodium  hydrate,  or  caustic  soda,  NaHO,  is  a  white,  opaque,  power- 
fully alkaline,  caustic  substance,  which  when  exposed  to  the  air 
absorbs  water  and  carbonic  acid,  becoming  converted  into  carbonate 
of  sodium.  In  its  chemical  action  upon  the  tissues  it  is  somewhat 
less  energetic  than  the  potassium  compound.  It  is  readily  soluble  in 
water,  with  the  evolution  of  heat,  yielding  a  highly  caustic  liquid. 
The  aqueous  solution,  according  to  Tuennermann,  contains  the  fol- 
lowing percentage  of  anhydrous  sodium  oxide,  NagO,  according  to  the 
different  specific  gravities  of  the  solution  : 


SPECIAL   CIIKMICATi    rROPEUTIKS.  86 

STRKNCiTIl    OK    AliUKOUS    SOLUTION.H    OF    80UA. 


„  Percentngo 

SP-  «>•.  Nh.0. 

1.428 ;W.22 

1.37a 2(;.o9 

1.327 22.% 

1  208 20.5r) 

1.277 18.73 

1.257 l"i-92 

1.228 14.50 


„      .,  Percentage 

op-  ^'■-  NiuO. 

1.194 12.00 

1.1(;8 10.87 

1.123 8.40 

1.094 0.04 

1.007 4.83 

1.033 2.41 

T.OlO 1.20 


The  mits  of  sodium  are  colorles.s,  unless  containing  a  colored 
acid.  They  are  readily  soluble  in  water,  and  more  disposed  than 
the  corresponding  compounds  of  potassium  to  unite  with  water  of 
crystallization.  The  crystallized  normal  carbonate  {protoearbon- 
aie),  as  also  several  other  salts,  contains  ten  molecules  of  water  of 
crystallization.  Many  of  its  salts  speedily  effloresce  wdien  exposed 
to  the  air. 

Special  Chemical  Properties.— When  caustic  soda,  or  any 
of  its  salts,  is  heated  in  the  inner  blow-pipe  flame,  it  communicates 
a  strong  yellow  color  to  the  outer  flame,  even  when  only  a  minute 
quantity  of  the  alkali  is  present.  The  presence  of  potassium  com- 
pounds, even  in  large  quantity,  does  not  obscure  this  reaction.  The 
same  coloration  is  developed  when  an  alcoholic  solution  of  the  alkali 
is  burned.  By  spectrum  analysis,  as  already  indicated,  the  reaction 
of  the  merest  traces  of  sodium  may  be  recognized. 

On  account  of  the  free  solubility  of  the  compounds  of  sodium, 
there  are  but  few  reagents  that  precipitate  it  even  from  concentrated 
solutions.  In  fact,— besides  the  coloration  of  flame,— antimoniate  of 
potassium  and  Polarized  Light  are  about  the  only  tests  at  pre.sent 
known  whereby  small  quantities  of  this  alkali  can  be  recognized. 

In  the  following  investigations  solutions,  of  pure  caustic  soda 
were  employed.  The  fractions  refer  to  the  fractional  part  of  a  grain 
of  the  anhydrous  alkali,  NaP,  in  solution  in  one  grain  of  water; 
and  the  results,  to  the  behavior  of  one  grain  of  the  solution. 

1.  Ifetantimonate  of  Potassium. 

A  solution  of  this  reagent  is  prepared  by  supersaturating  warm 
water  with  the  pure  salt  and  filtering  the  liquid  when  perfectly  cold. 
The  solution  should  always  be  freshly  prepared  when  required  for 
use. 

Metantimonate  of  potassium  throws  down  from  somewhat  con- 


86  SODA. 

centrated  solutions  of  caustic  soda  and  of  its  neutral  salts  a  white 
crystalline  precipitate  of  sodium  metantimonate,  XaSbOg.  The 
forms  of  the  crystals  produced  depend  very  much  upon  the  strength 
of  the  solution.  If  the  solution  has  an  acid  reaction,  it  should  be 
carefully  neutralized  with  potassium  carbonate  before  the  addition  of 
the  reagent,  since  otherwise  free  metantimonic  acid  or  acid  metanti- 
monate of  potassium  may  be  precipitated.  The  reaction  of  the  re- 
agent is  not  prevented  by  the  presence  of  moderate  quantities  of  salts 
of  potassium,  except  the  carbonate,  in  which  the  sodium  compound 
is  more  readily  soluble  than  in  pure  water. 

1.  -^  grain  of  sodium  oxide,  in  one  grain  of  water,  yields  with  the 

reagent  au  immediate  deposit  of  small  granules  and  rectangular 
plates ;  at  the  same  time  irregular  and  tooth-shaped  crystals,  as 
represented  in  the  upper  left  portion  of  Plate  II.,  fig.  1,  float 
upon  the  surface  of  the  mixture. 

2.  1    grain  yields  an  immediate   crystalline   precipitate,  consisting 

principally  of  small  elongated  rectangular  plates,  as  represented 
in  the  lower  portion  of  Plate  II.,  fig.  1. 

3.  _^_  grain  :  an  immediate  deposit,  consisting  chiefly  of  small  octa- 

hedral crystals,  as  illustrated  in  the  right-hand  portion  of  fig. 
1,  Plate  il. 

4.  .^4-g-  grain  :  almost  immediately  very  small  granules  appear,  and 

soon  there  is  a  quite  good  crystalline  deposit  of  small  plates  and 
octahedrons. 
5  _i^  o-rain :  after  a  little  time,  small  crystals  can  be  seen  with  the 
microscope ;  after  several  minutes,  a  very  satisfactory  deposit  to 
the  naked  eye.     If  the  mixture  be  stirred  with  a  glass  rod,  it 
yields  lines  of  granules  along  the  path  of  the  rod,  and  a  more 
copious  deposit. 
6.  yJ=j5-q  grain :  on  stirring  the  mixture,  crystals  become  perceptible 
to  the  microscope  in  about  five  minutes ;  in  about  fifteen  min- 
utes, they  become  quite  obvious  to  the  naked  eye;  and  after 
about  half  an  hour,  there  is  a  perfectly  satisfactory  crystalline 
deposit. 
Metantimonate  of  potassium  fails  to  precipitate  potassium  com- 
pounds and  ammonia,  even  from  concentrated  solutions ;  but  it  pro- 
duces precipitates  in  solutions  of  many  other  metals :  the  absence  of 
these,  therefore,  must  be  established  before  concluding  that  the  pre- 
cipitate consists  of  the  sodium  compound. 


SPKCIAI.    CHHMK'AT-    PROPERTIES.  87 

2.  Polarized  Light. 

Tliis  test,  which  was  tirst  suggested  by  Prof.  Andrews  {Chemical 
Gaz.f  X.  378),  is  founded  upon  the  fact  that  platinic  chloride,  and 
also  tlio  doul)le  chloride  of  potassium  and  i)latinuni,  when  placed  in 
the  dark  Held  of  the  polariscopc,  have  no  depolarizing  action,  whereas 
the  double  chloride  of  sodium  and  platinum  possesses  this  property  in 
a  remarkable  degree. 

To  apply  this  test,  its  author  recommended  the  following  method. 
Having  removed  other  bases  by  the  ordinary  methods  and  converted 
the  alkalies  into  chlorides,  a  drop  of  the  solution  is  placed  on  a  glass 
slide  and  a  very  small  quantity  of  a  dilute  solution  of  the  chloride 
of  platinum  added,  avoiding  as  far  as  possible  an  excess.  This  mix- 
ture is  evaporated  by  a  gentle  heat  till  it  begins  to  crystallize,  then 
placed  in  the  field  of  a  microscope  furnished  with  a  good  polarizing 
apparatus.  On  turning  the  analyzer  till  the  field  becomes  perfectly 
dark,  and  carefully  excluding  the  entrance  of  light  laterally,  the 
crystals  remain  invisible  if  only  the  potassium  compound  or  the  re- 
agent alone  be  present,  while  the  presence  of  the  slightest  trace  of 
sodium  is  at  once  indicated  by  the  beautiful  display  of  color  of  its 
platinum  double  salt,  2NaCl ;  PtCl^.  Prof.  Andrews  states  that 
in  this  manner  he  obtained  a  distinct  reaction  from  a  quantity  of 
chloride  of  sodium  representing  only  about  the  l-825,000th  of  a 
grain  of  the  anhydrous  alkali. 

In  applying  this  method,  instead  of  evaporating  the  mixture  by 
the  application  of  heat,  it  is  best  to  allow  it  to  evaporate  sponta- 
neously, as  it  thus  yields  much  larger  crystals  of  the  double  sodium 

salt. 

1.  Yrro  gi'ain  of  sodium  oxide  in  the  form  of  chloride,  in  one  grain 

of  water,  when  treated  with  a  very  small  quantity  of  the  reagent 
and  allowed  to  evaporate  spontaneously,  leaves  a  good  deposit 
of  long,  irregular  crystals  of  the  double  salt,  Plate  IL,  fig.  3. 
This  deposit,  under  the  polariscope,  furnishes  a  beautiful  display 
of  prismatic  colors. 

2.  y-ofoTo  grain '  quite  a  number  of  fine  crystals,  which  in  the  field 

of  the  polariscope  yield  very  satisfactory  results. 

3.  rooTool)  grain:  usually  yields  several  quite  distinct  and  satisfactory 

crystals.  Sometimes  the  deposit  is  in  the  form  of  thread-like 
groups,  which,  when  broken  up  by  the  point  of  a  needle,  form 


88  SODA. 

small  crystalline  plates.  In  this  manner,  these  thread-like 
masses  may  readily  be  distinguished  from  depolarizing  shreds  of 
dust,  which  are  sometimes  present. 

4.  -goT-ToT    g'^^ii  •     with    the    least    possible    quantity   of    reagent, 

yields  a  few  small  depolarizing  crystalline   plates.     Even  the 

1-1, 000,000th  of  a  grain  of  the  alkali  will  sometimes  yiekl 

quite  distinct  results. 

Before  applying  this  test,  the  examiner  should  be  certain  that 

any  potash  present  is  entirely  converted  into  chloride,  otherwise  he 

may  be  led  into  error. 

Picric  Acid. — It  is  usually  stated  by  writers  on  this  subject  that 
this  reagent  produces  no  precipitate  even  in  concentrated  solutions  of 
sodium  hydrate,  whereby  this  alkali  is  distinguished  from  potassium 
hydrate;  but  this  is  not  the  fact.  Thus,  one  grain  of  a  l-25th  so- 
lution of  the  former  alkali  yields  with  the  reagent,  within  a  little 
time,  a  quite  copious  crystalline  deposit,  Plate  I.,  fig.  6  ;  and  a  similar 
quantity  of  a  1-lOOth  solution  yields,  after  a  time,  a  quite  distinct 
crystalline  reaction.  Solutions  but  little  stronger  than  the  first  men- 
tioned become  converted  into  a  mass  of  crystals  by  the  reagent. 

The  crystalline  form  of  the  sodium  precipitate  will  usually  serve 
to  distinguish  it  from  the  potassium  compound,  as  also  from  that 
produced  in  solutions  of  ammonia. 

Tartaric  Acid  produces  in  very  coneentrated  solutions  of  the 
alkali,  especially  if  the  mixture  be  stirred,  a  white  crystalline  pre- 
cipitate of  acid  tartrate  of  sodium.  In  one  grain  of  a  1-lOth  solu- 
tion of  the  alkali  the  reagent  produces,  on  stirring  the  mixture,  after 
a  few  minutes,  a  mass  of  groups  of  bold  crystals,  Plate  II.,  fig.  2. 
One  grain  of  a  l-25th  solution,  under  the  same  circumstances,  yields, 
after  ten  or  fifteen  minutes,  a  quite  satisfactory  crystalline  deposit. 
If  this  mixture  be  not  stirred,  it  fails  to  yield  a  precipitate  even  after 
several  hours.  Solutions  but  little  more  dilute  than  this  fail  to  yield 
a  precipitate  under  any  condition  whatever,  even  after  many  hours. 

Platinic  Chloride  fails  to  precipitate  even  the  most  concen- 
trated solutions  of  sodium  compounds. 

As  a  micro-chemical  test  for  sodium,  A.  Streng  has  recently  ad- 
vised (1883)  to  treat  a  drop  of  the  solution  with  Uranium  Acetate, 
when  either  immediately,  or  on  spontaneous  evaporation  of  the  liquid, 
yellow  tetrahedral  crystals  of  uranium  sodium  acetate  are  formed. 


AMMONIA.  89 

Tlu>se  crystals  contain  only  G.6  per  cent,  of  sodium,  and  are  readily 
distini:;uislicd  from  the  rhombic  crystals  of  uranium  acetate  by  their 
action  on  polarized  lii^ht.  {Jour.  Cheni.  Soc.  Abstr.,  March,  1884, 
366.)  We  have  found  this  method  serve  for  the  detection  of  very 
minute  quantities  of  sodium  salts. 

Separation  from  Organic  Mixtures. — Caustic  soda  may  be 
separated  from  organic  mixtures  in  the  same  manner  as  already 
directed  for  the  recovery  of  caustic  potash  (ante,  83). 

Since,  according  to  the  researches  of  E.  Donath,  commercial 
caustic  soda  sometimes  contains  minute  quantities  of  arsenic,  even 
to  the  extent  of  0.16  per  cent,  of  arsenic  acid,  this  contamination 
might  sometimes  give  rise  to  embarrassment  in  poisoning  by  the 
caustic  alkali.     {Jour.  Chem.  Soc.  Abstr.,  1881,  856.) 

Section  III. — Ammonia. 

General  Chemical  Nature. — Ammonia,  in  its  pure  state,  is 
a  gaseous  compound  of  Xitrogen  and  Hydrogen,  XHg,  having  a  very 
pungent  odor  and  powerfully  alkaline  reaction.  The  gas  is  readily 
absorbed  by  water,  which  is  thereby  increased  in  volume  and  dimin- 
ished in  density ;  at  a  temperature  of  10°  C.  (50°  F.),  according  to 
Davy,  this  fluid  takes  up  about  670  times  its  volume  of  the  gas,  and 
then  has  a  density  of  0.875.  A  solution  of  this  kind  constitutes 
common  aqua  ammonise,  and  is  usually  regarded  as  a  hydrate  of 
ammonium,  XH^jHO.  According  to  Sir  H.  Davy,  the  following 
table  exhibits  the  percentage  by  weight  of  ammonia  gas  in  pure 
aqueous  solutions  of  different  specific  gravities : 

STRENGTH    OF    AQVEOUS    SOLUTIONS    OF    AMMONIA. 
Sp.Gr.  Percentage  g^  g^_  Per^^ntage 

0.875 32.30  0.938 15.88 

0.885 29.25  0.943 14.53 

0.900 26.00  0.947 13.46 

0.905 25.37  0.951 12.40 

0.916 22.07  0.954 11.56 

0.925 19.54  0.959 10.17 

0.932 17.52  0.963 9.50 

Aqua  ammonise,  when  pure,  is  colorless,  has  a  peculiar  powerfully 
pungent  odor,  and  a  strong  alkaline  reaction,  immediately  restoring 
the  blue  color  of  reddened  litmus-paper ;  on  warming  the  blued 
paper,  the  red  color  reappears,  from  the  dissipation  of  the  alkali. 


90  AMMONIA. 

On  heating  a  solution  of  ammonia,  the  gas  is  rapidly  expelled  with 
effervescence;  when  the  liquid  is  evaporated  to  dryness  it  leaves  no 
residue,  unless  foreign  matter  be  present. 

The  salts  of  ammonia,  usually  named  ammonium  salts,  are  color- 
less, and  readily  volatilized  upon  the  application  of  heat.  With  few 
exceptions,  they  are  freely  soluble  in  water.  The  fixed  caustic  al- 
kalies readily  decompose  them,  with  the  evolution  of  free  ammonia. 
^  Special  Chemical  Properties. — Solutions  of  free  ammonia 
are  readily  recognized  by  their  peculiar  odor.  The  salts  of  this  base, 
when  heated  on  platinum  foil,  are  completely  dissipated,  unless  they 
contain  a  fixed  acid  or  foreign  matter,  in  which  respect  they  differ 
from  the  salts  of  the  fixed  alkalies.  When  their  solutions  are  treated 
with  potassium  or  sodium  hydrate,  or  with  hydrate  of  lime,  and  the 
mixture  gently  warmed  in  a  test-tube,  the  presence  of  the  ammonia 
eliminated  by  the  decomposition  may  be  recognized  by  its  odor ;  as 
also  by  its  alkaline  reaction  upon  moistened  reddened  litmus-paper ; 
and  also  by  the  production  of  white  fumes  of  ammonium  chloride 
when  a  glass  rod  moistened  with  dilute  hydrochloric  acid  is  held 
over  the  mouth  of  the  tube.  By  suspending  a  slip  of  moistened 
reddened  litmus-paper  within  the  tube  and  closing  its  mouth,  the 
presence  of  very  minute  traces  of  the  alkali  may,  at  least  after  a 
time,  be  recognized. 

The  behavior  of  solutions  of  ammonia  and  of  some  of  its  salts, 
when  treated  with  nitrate  of  silver  and  corrosive  sublimate,  has 
already  been  pointed  out  [ante,  73).  When  the  alkali  is  added  in 
excess  to  solutions  of  salts  of  copper,  the  liquid  assumes  a  charac- 
teristic blue  color. 

In  the  following  investigations  of  the  reactions  of  ammonia,  so- 
lutions of  pure  chloride  of  ammonium  were  employed.  The  frac- 
tions refer  to  the  amount  of  gaseous  ammonia  present  in  one  grain 
of  the  solution,  which  was  the  quantity  employed  for  each  reaction, 
unless  otherwise  stated. 

1.  Plaiinio  Chloride. 

This  reagent  produces  in  neutral  and  slightly  acid  solutions  of 
ammonia  a  yellow  octahedral  crystalline  precipitate  of  the  double 
chloride  of  ammonium  and  platinum,  2NH4CI ;  PtCl^,  which  is  but 
sparingly  soluble  in  diluted  mineral  acids,  and  in  the  free  alkalies. 
In   appearance  the  precipitate   closely  resembles  the  corresponding 


SrEClAL    CIIKMU.AL    I'UOl'KUTI KS.  91 

coinpoiiiul  of  potassliiin.  A  given  quantity  ofanitnonia  in  tlie  form 
of  c'lilorido  yields  with  the  reagent  a  larger  (juantity  <A'  the  (l(jul)le 
salt  than  the  same  (jiiantity  of  caustic  potash  :  ope  part  by  weight 
of  the  former  yielding  13.1  j)arts,  and  one  part  of  the  latt(!r  only  5.2 
parti!,  of  the  double  eompoiind. 

1.  ^  grain  of  ammonia,  in  one  grain  of  water,  when  treated  with 

the  reagent,  the  mixture  immediately  becomes  converted  into  an 
almost  solid  mass  of  crystals.  The  precipitate  is  much  more 
copious  than  that  from  a  similar  solution  of  a  potassium  com- 
pound, but  the  crystals  are  somewhat  smaller,  and  a  portion  of 
the  deposit  is  in  the  form  of  granules. 

2.  YWo   gi*'^i»  '  i"  a  ■^'cry  few  moments  a  very  copious  crystalline 

deposit. 

3.  Yt()  &i"^i"  •  tli6  precipitate  begins  to  appear  within  a  few  moments, 

and  in  a  little  time  there  is  a  quite  good  octahedral  deposit, 
very  similar  to  that  from  a  1-lOOth  solution  of  potassium  oxide 
(Plate  I.,  fig.  1). 

4.  g-^  grain :  crystals  appear  in  less  than  half  a  minute,  and  in  a 

little  time  they  are  quite  copious. 

5.  Y^-g-  grain  :  in  about  three  minutes  crystals  are  just  perceptible; 

in  about  five  minutes  the  deposit  is  quite  satisfactory.  The  for- 
mation of  the  precipitate  is  somewhat  hastened  by  stirring  the 
mixture  with  a  glass  rod. 

6.  YWTo  grain  :  in  about  eight  minutes  crystals  are  perceptible  to  the 

microscope,  and  soon  after  they  become  quite  obvious  to  the 
naked  eye,  especially  along  the  margin  of  the  mixture;  after 
about  half  an  hour  there  is  a  quite  satisfactory  deposit. 
Solutions  but  little  more  dilute  than  the  last  mentioned  fail  to 
yield  a  precipitate  even  after  many  hours. 

Fallacies. — The  method  of  distinguishing  the  double  chloride  of 
ammonium  and  platinum  from  the  corresponding  potassium  com- 
pound has  already  been  pointed  out  under  the  special  consideration 
of  the  latter  {ante,  77).  This  reagent  fails  to  produce  a  precipitate 
even  in  the  most  concentrated  solutions  of  sodium  salts. 

2.   Tartaric  Acid,  and  Tartrate  of  Sodium. 

These  reagents  produce  in  neutral  solutions  of  ammonia,  when 
not  too  dilute,  a  white  crystalline  precipitate  of  acid  tartrate  of  am- 
monium, NH^,HCiH40g,  which  in  appearance  is  v^ery  similar  to  the 


92  AMMONIA. 

corresponding  salt  of  potassium,  but  somewhat  more  soluble  in  water. 
It  is  soluble  in  the  free  alkalies  and  in  dilute  mineral  acids. 

1.  ^  grain  of  the  alkali  yields  with  free  tartaric  acid  no  immediate 

precipitate,  but  in  a  little  time  crystals  begin  to  separate,  and 
after  a  few  minutes  there  is  a  very  satisfactory  deposit,  the 
crystals  having  the  same  form  as  those  from  potassium  oxide, 
Plate  I.,  fig.  2.  The  acid  tartrate  of  sodium  produces  much  the 
same  results,  but  the  forms  of  the  crystals  are  then  similar  to 
those  illustrated  in  Plate  I.,  fig.  3. 

2.  Y^  grain :    after  several   minutes   granules  and  small  crystals 

appear,  and  after  some  minutes  more  there  is  a  quite  good  crys- 
talline deposit,  chiefly  confined,  however,  to  the  margin  of  the 
mixture.  With  tartrate  of  sodium,  the  precipitate  is  more 
prompt  in  appearing  and  becomes  more  abundant;  the  forms 
of  the  crystals  are  then  the  same  as  before  by  this  form  of  the 
reagent. 

3.  2^  grain :  after  ten  or  fifteen  minutes  some  few  granules  form 

along  the  margin  of  the  mixture;  in  about  half  an  hour  the 
deposit  becomes  quite  satisfactory.  The  sodium  reagent  pro- 
duces a  more  prompt  and  satisfactory  reaction.  The  formation 
of  the  precipitate  from  this,  as  well  as  from  the  preceding  solu- 
tions, is  much  facilitated  by  stirring  the  mixture. 

4.  g-g-Q  grain  yields  with  tartrate  of  sodium,  after  stirring  the  mix- 

ture some  minutes,  a  distinct  granular  deposit,  which,  after  a 
time,  becomes  quite  satisfactory. 
There  is  nothing  in  the  physical  appearance  of  the  tartrate  of 
ammonium  to  distinguish  it  from  the  corresponding  precipitate  pro- 
duced from  solutions  of  potassium. 

3.  Picric  Acid. 
An  alcoholic  solution  of  picric  acid   produces  in  neutral  solu- 
tions of  salts  of  ammonium  a  yellow  crystalline  precipitate  of  ammo- 
nium picrate,  NH4,CgH2(N02)30,  which  is  insoluble  in  excess  of  the 
reagent. 

1.  -^  grain  of  the  alkali  yields  an  immediate  amorphous  precipitate, 
which  in  a  little  time  becomes  a  mass  of  yellow  crystals.  The 
form  of  the  crystals  is  quite  different  from  that  of  those  pro- 
duced by  the  reagent  from  solutions  of  either  of  the  fixed 
alkalies. 


SPECIAL    CHEMKAL    I'KOI'ERTIKS.  93 

2.  j-^jy  tiniiii :  almost   immediately  crystals  begin  to  separate,  and  in 

a  little  time  there  is  a  (juite  good  deposit.  Under  the  microscope, 
the  crystals  present  the  apj)earances  illnstrated  in  Plate  I.,  fig. 
5,  which  readily  distinguish  them  from  the  corresponding  salts 
of  potassinm  and  sodium. 

3.  ^hii  ^^'''li'i :   '"  'I  few  moments  small  rough  needles  begin  to  form, 

and  very  soon  there  is  a  good  crystalline  j)recij)itate,  in  form 
quite  unlike  that  from  potassium  compounds. 

4.  -j-J-^  grain  :   in  a  few  minutes  needles  begin  to  separate  along  the 

margin  of  the  drop,  and  after  a  little  time  there  is  a  satisfactory 
deposit. 

5.  yi-y  grain :  after  some  minutes,  small  needles  appear ;  after  some 

minutes  more,  there  is  a  quite  satisfactory  deposit  of  needles, 
plates  and  cubes,  which  might  readily  be  confounded  with  the 
deposit  from  dilute  solutions  of  potassium  compounds. 

4.  Nesslei^'s  Test. 

When  a  solution  of  iodide  of  potassium  and  mercuric  iodide  in 
the  ])resence  of  potassium  hydrate  is  acted  upon  by  ammonia,  the 
latter  is  decomposed  with  the  formation  of  an  insoluble  compound, 
known  as  dimercur-ammonium  iodide,  NHg2l,H20. 

The  test-fluid  is  prepared  by  dissolving  20  parts  by  weight  of 
pure  potassium  iodide  in  50  parts  of  pure  water,  and  adding  mer- 
curic iodide  to  the  solution  until  it  is  no  longer  dissolved,  which  will 
require  about  30  parts  of  the  mercuric  salt.  The  liquid  will  now 
contain  the  double  iodide  of  potassium  and  mercury,  2KI ;  Hglg. 
The  solution  is  diluted  with  three  volumes  of  water,  and  the  mixture 
allowed  to  stand  some  hours,  when  any  excess  of  the  mercuric  iodide 
will  separate  in  the  crystalline  form.  The  fluid  is  then  filtered,  and 
two  measures  of  the  filtrate  mixed  with  three  measures  of  a  strong 
solution  of  potassium  hydrate;  this  mixture  is  employed  as  the  re- 
agent. Should  the  liquid  become  turbid  upon  the  addition  of  the 
potash  solution,  it  is  again  filtered. 

In  the  absence  of  mercuric  iodide,  the  reagent  mixture  may  be 
prepared  by  treating  a  solution  of  potassium  iodide  with  a  saturated 
solution  of  mercuric  chloride,  until  a  slight  permanent  precipitate  is 
formed;  a  strong  solution  of  potassium  hydrate  is  then  added,  and 
the  mixture  allowed  to  stand  until  the  liquid  becomes  clear,  when  it 
is  decanted. 


94  AMMONIA. 

1.  YoT  gJ'ain  of  ammonia  as  chloride,  in  one  grain  of  water,  yields, 

witli  a  drop  of  the  reagent,  a  very  copious,  beautiful  orange- 
colored  amorphous  precipitate,  most  of  which  dissolves,  with 
the  production  of  a  colorless  solution,  in  excess  of  free  ammonia, 
and  of  chloride  of  ammonium,  leaving  a  slight,  cream-colored 
residue.  The  precipitate  is  readily  soluble,  to  a  colorless  solu- 
tion, in  hydrochloric  acid. 

2.  xoVo  grain  yields  a  quite  copious  precipitate,  having  a  fine  orange 

color. 

3.  Yir.Wo"  grain  :  a  very  good,  reddish-yellow  deposit.     Five  fluid- 

grains  of  the  solution  yield  a  fine  orange  precipitate. 

4.  5-0, VoT  grain:   an  immediate  yellow  turbidity,  which  very  soon 

assumes  an  orange  tint,  followed  by  a  good  flocculent  precipitate, 
having  a  light-yellow  color.  Ten  fluid-grains  of  the  solution, 
with  a  drop  of  the  reagent,  yield  an  almost  immediate,  orange- 
colored  muddiness,  which  slowly  subsides  to  a  deposit  of  the 
same  color, 

5.  YlTo^-o-oT  grain  :  an  immediate  cloudiness,  and  in  a  very  little  time 

the  mixture  contains  suspended  flakes,  which  have  a  dirty-white 
color.  Five  fluid-grains  of  the  solution  yield  a  bright-yellow 
turbidity,  and  soon  the  mixture  acquires  a  slight  orange  tint. 

6.  g-oi^oiro"  grain :  after  a  little  time,  a  just  perceptible  cloudiness. 

Five  fluid-grains  of  the  solution  very  soon  assume   a   pale- 
yellow  color,  which  on  heating  the  mixture  is  changed  to  a  very 
slight  orange  hue. 
'^*  T.TTo'.Too'  solution  :  five  fluid-grains  of  the  solution,  after  a  little 
time,  assume  a  very  pale-yellow  color,  which  on  the  application 
of  heat  is  changed  into  the  slightest  perceptible  tint  of  orange. 
The  color  of  this,  and  of  other  dilute  solutions,  is  best  seen  by 
transmitted  light. 
The  extreme  sensibility  of  this  test  is  explained  by  the  circum- 
stance that  17  parts  by  weight  of  ammonia  yield  559  parts  of  the 
mercury  compound,  in  accordance  with  the  following  reaction : 
NH3  -f-  2(2KI ;  Hgl^)  +  3K HO  =  NHg2l,H20  +  7KH-  2H2O. 
According  to  J.  ISTessler,  the  presence  of  alkaline  chlorides  and 
oxysalts  has  no  injurious  influence  upon  the  reaction  of  this  reagent; 
and   iodide  of   potassium  is  injurious  only  when  sufficient  caustic 
potash  has  not  been  added.     But  the  reaction  is  not  produced  in  the 
presence  of  potassium  cyanide  and  potassium  sulphide,  even  in  con- 


SEPARATION    FKOM    ORGANIC   MIXTURES.  96 

centratetl  soliitious  of  ainnioiiia  and  tlie  presence  of  great  excess  of 
potassium  hydrate. 

Mercuric  Chloride  (HgCl,)  produces  in  solutions  of  ammo- 
nium hydrate,  even  wlien  liigiily  diluted,  a  white  precii)itate  of  mercur- 
ammonlum  chloride,  XH  JlgCl";  thus  :  2XH3  +  HgCI,  =  XH^HgCl  + 
NH^Cl.  When  the  ammonia  is  present  in  the  form  of  a  salt,  a  little 
sodium  carbonate  solution  should  be  previously  added  to  the  mer- 
curic reagent,  both  solutions  being  quite  dilute.  This  mixture  sepa- 
rates from  solutions  of  free  ammonia  and  its  salts  the  precipitate  be- 
fore mentioned  in  combination  with  mercuric  oxide,  NH2HgCI,HgO. 
The  reaction  will  now  manifest  itself  even  in  solutions  containing 
only  the  minutest  trace  of  the  alkali.  This  reaction  was  fii-st  observed 
by  M.  Bohlig. 

Phospho-molybdate  of  SoDiUii,  according  to  Sonnenschein 
{Chem.  Gaz.,  x.  411),  will  readily  detect  the  presence  of  one  part  of 
chloride  of  ammonium  in  10,000  parts  of  water.  The  reagent  is 
prepared  by  igniting  the  yellow  precipitate  produced  by  adding 
molybdate  of  ammonium  to  an  acidulated  solution  of  sodium  phos- 
phate to  expel  the  ammonia;  any  molybdic  acid  reduced  in  this 
operation  is  reoxidized  by  nitric  acid,  the  excess  of  which  is  expelled 
by  heat.  The  residue  is  then  dissolved  in  sodium  carbonate,  the 
solution  supersaturated  with  hydrochloric  acid,  and  the  mixture 
heated,  after  which  any  precipitate  that  has  formed  is  redissolved 
by  the  addition  of  more  acid. 

This  liquid,  when  employed  as  a  reagent,  produces  in  solutions  of 
salts  of  ammonia  a  yellow  precipitate  of  phospho-molybdate  of  am- 
monium which,  according  to  Sonnenschein,  contains  only  4.411  per 
cent,  of  gaseous  ammonia.  The  reagent  produces  a  similar  yellow 
precipitate  in  tolerably  concentrated  solutions  of  salts  of  potassium; 
but  it  fails  to  precipitate  solutions  of  sodium  salts. 

Metantiraonate  of  Potassium  produces  no  precipitate,  even  in  con- 
centrated solutions  of  salts  of  ammonia  or  of  the  free  alkali. 

Separation  from  Organic  Mixtfees. 

Unless  the  ammonia  be  present  only  in  extremely  small  quantity 
or  combined  with  an  acid,  the  liquid  will  have  an  alkaline  reaction 


96  AMMONIA. 

and  give  out  the  odor  of  the  alkali.  Ammonia  and  its  carbonate 
may  be  separated  from  organic  solutions  by  distilling  the  liquid,  at 
a  moderate  heat,  in  a  retort  the  beak  of  which  is  provided  with  a 
perforated  cork  carrying  a  small  tube,  which  is  bent  at  an  obtuse 
angle  and  made  to  dip  beneath  the  surface  of  a  very  small 
quantity  of  pure  water,  contained  in  a  well-cooled  receiver.  Any 
of  the  alkali  or  its  carbonate  present  will  be  vaporized  by  the  heat 
and  pass  along  with  the  vapor  of  water  into  the  receiver ;  the  solu- 
tion thus  obtained  may  be  tested  in  the  ordinary  manner. 

If  after  distilling  over  about  one-eighth  of  the  contents  of  the 
retort  no  ammonia  yet  appears  in  the  distillate,  it  may  be  concluded 
that  none  of  the  free  alkali  or  its  volatile  salt  is  present.  It  may, 
however,  be  present  in  the  form  of  some  of  its  more  fixed  salts.  To 
ascertain  this,  the  contents  of  the  retort  are  treated  with  strong  alco- 
hol, which  will,  in  part  at  least,  coagulate  the  organic  matter  ;  the 
mixture  is  then  filtered,  the  filtrate  treated  with  potassium  hydrate  or 
hydrate  of  lime,  and  distilled  as  before.  Any  ammoniacal  salt  pres- 
ent will  now  be  decomposed  by  the  alkali  added,  with  the  evolution  of 
free  ammonia,  which  will  appear  in  the  distillate.  In  some  instances 
it  is  best  to  replace  the  pure  water  placed  in  the  receiver  by  a  very 
dilute  solution  of  hydrochloric  acid,  whereby  the  ammonia  will  be 
more  effectually  absorbed,  in  the  form  of  chloride  of  ammonium. 

If  the  mixture  under  examination  contains  organic  matter  in  a 
state  of  decomposition,  this  may  give  rise  to  ammonia.  In  mixtures 
of  this  kind  it  may  be  difficult  or  even  impossible  to  decide  the  true 
source  of  the  ammonia.  If  it  be  the  contents  of  the  stomach  that 
are  thus  examined,  the  quantity  of  the  alkali  recovered  and  the  jpost- 
mortem  appearances  may  readily  decide  its  origin. 

Quantitative  Analysis. — This  may  be  effected  by  precipi- 
tating the  alkali  in  the  form  of  double  chloride  of  ammonium  and 
platinum,  and  treating  the  precipitate  in  the  same  manner  as  directed 
for  the  estimation  of  potassium  compounds  {ctnte,  84).  The  double 
ammonium  salt  contains  7.62  per  cent,  by  weight  of  pure  ammonia 
(NH3). 

Every  17  grains  of  real  ammonia  correspond  to  52.6  grains  of  the 
most  concentrated  aqua  ammonide,  which  measure  a  few  drops  over  one 
fluid-drachm.  Or,  three  parts  by  weight  of  a  concentrated  aqueous  so- 
lution of  the  gas  contain  about  one  part  by  weight  of  free  ammonia. 


THE   MINERAL   ACIDS.  97 


CHAPTER      11. 

THE   MINERAL   ACIDS:    SULPHURIC,  NITRIC,  AND   HYDRO- 
CHLORIC. 

General  Nature  and  Effects. — The  above-named  mineral 
acids  form  a  group  of  compounds  the  members  of  which  are  quite 
similar,  both  in  respect  to  their  general  chemical  properties  and  their 
effects  upon  the  animal  system.  They  possess  the  jiroperty  of  acidity 
in  the  most  eminent  degree,  such  as  reddening  blue  litmus,  perfectly 
neutralizing  free  alkalies,  and  decomposing  the  salts  of  other  acids. 
They  are  more  or  less  decomposed  when  brought  in  contact  with 
many  of  the  metals,  such  as  zinc,  iron,  copper,  and  mercury,  with 
the  formation  of  their  respective  salts.  Sometimes  this  decomposi- 
tion takes  place  at  ordinary  temj)eratures,  but  at  other  times  only 
upon  the  application  of  heat.  Most  of  the  salts  of  these  acids  are 
readily  soluble  in  water. 

In  their  powers  to  corrode  and  destroy  organic  substances  the 
mineral  acids  stand  pre-eminent.  When  brought,  in  their  some- 
what concentrated  state,  in  contact  with  living  animal  tissues,  they 
rapidly  destroy  their  organization  and  vitality;  in  this  manner  they 
may  speedily  occasion  death  by  their  direct  chemical  action.  Due 
to  this  action,  they  also  speedily  affect  or  entirely  destroy  various 
articles  of  clothing  with  which  they  come  in  contact :  this  property 
is  sometimes  of  considerable  importance  in  a  medico-legal  point  of 
view. 

Numerous  instances  are  recorded  in  which  these  substances  occa- 
sioned death  ;  but,  with  few  exceptions,  the  poison  was  taken  either 
with  suicidal  intent  or  as  the  result  of  accident.  In  fact,  from  their 
immediate  and  powerfully  corrosive  action  on  the  mouth,  there  is 
perhaps  no  poison  which,  for  criminal  purposes,  could  not  be  resorted 
to  with  greater  safety  from  detection  than  either  of  these  acids ;  yet 
cases  are  not  wanting  in  which  they  were  thus  employed. 

7' 


98  SULPHUEIC  ACID. 

Section  I. — Sulphuric  Acid. 

This  acid  has  long  been  known  under  the  name  of  oil  of  vitriol, 
which  name  it  received  from  the  fact  that  it  was  prepared  from  green 
vitriol,  or  ferrous  sulphate.  As  met  with  in  the  shops,  it  is  a  dense, 
powerfully  acrid  and  corrosive,  oily  liquid,  with  frequently  a  more 
or  less  brownish  color.  AVhen  brought  in  contact  with  organic 
substances,  it  speedily  chars  them.  In  proportion  as  it  is  diluted 
with  water,  it  loses  its  oily  appearance  and  power  of  acting  upon 
organic  tissues.  As  a  poison,  it  has  been  principally  used  in  the 
form  of  the  commercial  acid,  yet  instances  of  poisoning  by  sulphate 
of  indigo,  which  is  a  solution  of  indigo  in  the  concentrated  acid, 
and  by  ar^omatic  sulphuric  acid  of  the  Pharmacopoeias,  have  also 
occurred. 

Instances  of  poisoning  by  this  acid  have  been  of  much  more 
frequent  occurrence  than  by  either  of  the  other  mineral  acids.  But, 
as  already  intimated,  it  has  rarely  been  administered  criminally.  Of 
twelve  cases  of  poisoning  by  this  substance  collected  by  Dr.  Cozzi, 
in  a  hospital  in  Florence,  eleven  were  the  result  of  suicide.  Dr. 
Christison  has  collected  several  instances  in  which  children  were 
murdered  by  the  acid  being  poured  doMm  the  throat.  A  case  is  also 
reported  in  which  a  man  was  murdered  in  a  similar  manner  while 
he  lay  asleep ;  and  another,  in  which  it  was  thus  administered  to  a 
woman  while  she  was  intoxicated.  A  singular  practice  of  secretly 
throwing  the  acid  upon  persons  for  the  purpose  of  disfiguring  them 
or  of  destroying  their  dress  has  been  of  not  unfrequent  occurrence, 
both  in  this  country  and  in  Europe. 

Sympto]SIS. — The  direct  eflPects  of  sulphuric  acid  will,  of  course, 
depend  much  upon  the  degree  of  its  concentration,  and  the  quantity 
taken.  When  taken  in  its  concentrated  state,  all  the  soft  parts 
of  the  mouth  and  throat  are  immediately  more  or  less  corroded 
and  destroyed,  and  assume  a  white  appearance;  and  if  the  poison 
has  been  swallowed,  the  lining  membrane  of  the  oesophagus  and 
stomach  will  be  acted  upon  in  the  same  manner.  These  effects  will 
be  followed  with  intense  burning  pain  in  the  mouth,  throat,  and 
stomach,  alteration  of  voice,  gaseous  eructations,  and  violent  vomit- 
ing. The  vomited  matters  have  usually  a  brownish  or  black  color, 
strongly  acid  properties,  and  contain  disorganized  membrane  and 
blood.     As  the  case  advances,  there  will  be  excruciating  pain  in  the 


PIIYSIOUKSICAI.    EFB'ECTS.  99 

bowels,  impaired  respiration,  (liflieiilty  of  swallowing,  coldness  of 
tlie  oxtreniitics,  and  great  prostration.  The  pulse  becomes  weak 
anil  irregular,  the  countenance  ghastly,  and  the  body  covered  with 
eold  })erspiration.  The  bowels  are  usually  much  constipated,  and 
the  urine  scanty.  The  inside  of  the  mouth  and  throat  frequently 
becomes  covered  with  sloughs.  The  mental  faculties  usually  remain 
unimpaired. 

Such  are  the  symi)toms  usually  observed  in  poisoning  by  this 
acid  in  its  concentrated  state;  but  it  is  obvious  that  they  may  not  all 
be  present  in  a  given  case.  The  vomiting,  which  in  most  instances 
is  either  immediate  or  within  a  very  short  period,  has  been  delayed 
for  half  an  hour  or  longer.  The  action  of  the  acid  may  be  confined 
to  the  mouth,  the  poison  having  been  thrown  out  without  any  portion 
of  it  being  swallowed.  In  such  cases,  however,  it  may  produce 
death  by  asphyxia,  from  the  closure  of  the  air-passages.  On  the 
other  hand,  the  mouth  may  escape  the  local  action  of  the  acid,  it 
having  been  administered  in  a  spoon  passed  back  into  the  throat,  as 
in  a  case  cited  by  Dr.  Taylor.  If  the  acid  has  come  in  contact  with 
the  lips  or  other  parts  of  the  external  skin,  they  at  first  present  a 
white  appearance,  which  afterward  becomes  yellowish-brown. 

In  a  case  reported  by  Mr.  Corfe,  a  man  swallowed  about  half  a 
pint  of  the  acid,  but  ^  large  portion  of  it  was  immediately  rejected. 
The  patient  suffered  intense  agony,  and  soon  after  the  extremities 
were  cold  and  mottled,  the  pulse  small  and  feeble;  the  epithelium  on 
the  tongue  and  lips  was  partially  removed,  and  that  on  the  fauces 
more  extensively  detached.  Death  took  place  twenty  hours  after  the 
acid  had  been  swallowed.  In  another  case,  a  woman,  aged  fifty  years, 
took  about  half  an  ounce  of  the  acid.  The  moment  it  reached  her 
throat,  she  seemed  to  be  strangled,  and  fell.  In  about  an  hour  after- 
ward, vomiting  having  occurred  several  times,  she  complained  of 
burning  pain  in  the  region  of  the  stomach,  but  after  an  hour  or  two 
the  pain  entirely  disappeared.  The  pulse  was  small  and  intermitting ; 
the  mouth  presented  the  appearance  of  having  been  smeared  with 
milk,  and  the  epiglottis  was  much  enlarged,  but  the  voice  was  almost 
natural.  The  patient  gradually  sank,  and  died  about  forty  hours 
after  taking  the  acid,  the  mind  remaining  clear  until  death. 

When  swallowed  in  its  diluted  state,  sulphuric  acid  produces 
much  the  same  symptoms  as  those  just  described,  only  that  they  are 
less  prompt  in  appearing,  and  the  local  action  of  the  poison  is  less 


100  SULPHURIC  ACID. 

violent.  The  extent  of  this  difference  will,  of  course,  depend  upon 
the  degree  of  dilution  of  the  acid. 

Period  when  Fatal. — In  fatal  poisoning  by  this  acid,  death  usually 
takes  place  in  from  twelve  to  thirty-six  hours ;  but  this  event  has 
occurred  within  an  hour,  and  again  it  has  been  delayed  for  weeks, 
and  even  months.  Dr.  Christison  cites  a  case  in  which  a  child, 
while  attempting  to  swallow  strong  sulphuric  acid  by  mistake  for 
water,  died  almost  immediately,  to  all  appearances  from  suffocation 
caused  by  contraction  of  the  glottis ;  it  was  ascertained  after  death 
that  none  of  the  poison  had  reached  the  stomach.  (Ojj.  cit.,  132.) 
Mr.  Traill  reports  the  case  of  a  washerwoman,  who  took  by  mistake 
a  wineglassful  of  the  commercial  acid,  having  a  specific  gravity  of 
1.833,  and,  although  actively  treated,  died  in  one  how  afterward. 
After  death,  a  perforation  was  found  in  the  stomach,  and  the  perito- 
neum was  greatly  inflamed  from  the  escape  of  the  acid  from  the 
stomach.  An  instance  is  also  related  by  Prof.  Casper,  in  which  the 
poison,  administered  by  an  unnatural  mother  to  her  own  child,  aged 
one  year  and  a  half,  caused  death,  in  spite  of  the  antidotes  adminis- 
tered, in  one  hour.  {^Forensic  Jledicine,  ii.  75.)  These  are  the  most 
rapidly  fatal  cases  yet  recorded.  Xot  less  than  three  cases,  however, 
are  reported  in  wdiich  death  occurred  in  two  hours;  and  several  in 
which  death  took  place  in  from  three  to  five  hours.  In  three  other 
cases,  death  took  place  in  four  and  eleven  days  respectively  in  adults, 
and  in  the  case  of  a  child  seventeen  months  old,  in  seven  hours. 

In  poisoning  by  sulphuric  acid,  as  in  the  case  of  the  caustic  alka- 
lies, the  patient  may  recover  from  the  immediate  effects  of  the  poison, 
and  yet  die  from  secondary  causes  long  afterward.  In  such  cases, 
nervous  symptoms  and  general  derangement  of  the  assimilating  or- 
gans usually  manifest  themselves,  and  death  is  the  result  either  of 
chronic  inflammation  of  the  stomach  and  bowels,  or  of  stricture  of 
some  part  of  the  alimentary  tube.  Several  instances  are  reported  in 
which  death  did  not  take  place  until  from  the  fifteenth  to  the  twentieth 
day  after  the  poison  had  been  taken ;  and  Dr.  Beck  quotes  a  case 
not  fatal  until  after  the  lapse  of  two  months.  In  an  instance  reported 
by  Dr.  Wilson,  life  was  prolonged  for  over  ten  months.  During  the 
progress  of  this  case,  the  thickened  lining  membrane  of  the  oesoph- 
agus came  away  in  the  form  of  a  firm  cylindrical  tube,  eight  or  nine 
inches  in  length.  The  most  protracted  case  in  this  respect  yet  re- 
corded is  that  quoted  by  Dr.  Beck  [Med.  Jur.,  ii.  472),  in  which 


ANTIDOTES.  101 

the  i)atient  survived  the  taking  of"  the  poison  two  yearn,  when  death 
supervened  from  the  etteets  of  stricture  of  the  oesophagus. 

Fatal  Quantity. — The  effects  of  given  quantities  of  sulpliuric 
acid  have  by  no  means  been  uniform.  They  will  be  influence<l 
much  by  the  condition  of  the  stomach,  as  to  the  presence  of  foo<l, 
and  the  deirrec  of  concentration  of  the  acid,  as  also,  of  course,  by  the 
promptness  with  which  remedies  are  employed.  In  many  instances 
it  is  difficult  to  determine  exactly  how  much  of  the  poison  has  been 
retained  in  the  body,  even  when  the  quantity  originally  taken  is 
accurately  known,  since  much  of  it  is  often  rejected  from  the  mouth 
as  soon  as  taken. 

The  smallest  fatal  dose  yet  recorded  is  in  a  case  quoted  by  Dr. 
Christison,  in  which  half  a  teaspoouful,  or  about  thirty  minims,  of  the 
concentrated  acid  caused  the  death  of  a  child,  one  year  old,  in  twenty- 
four  hours.  The  same  writer  quotes  another  instance,  in  which  (me 
drachm,  taken  by  a  stout  young  man,  proved  fatal  in  seven  days.  (Op. 
cit.,  131.)  In  a  case  already  mentioned,  about  one  drachm  and  a  half 
of  the  acid,  poured  into  the  mouth  of  a  man  while  asleep,  caused 
death  in  forty-seven  hours. 

On  the  other  hand,  recovery  has  not  unfrequently  taken  place 
after  large  doses  of  the  acid  had  been  swallowed.  Thus,  not  less 
than  two  instances  of  this  kind  are  related,  in  each  of  which  two 
ounces  of  the  concentrated  acid  had  been  taken.  And  Dr.  Beck 
quotes  a  case  in  which  a  man  recovered  after  having  swallowed  four 
ounces  (whether  by  weight  or  by  measure  not  stated).  This  is  the 
largest  dose  that  we  find  recorded  from  which  there  was  recovery. 

Treatment. — There  are  many  substances  that  will  perfectly 
neutralize  this  acid,  yet  on  account  of  its  very  rapid  local  action,  at 
least  in  its  concentrated  state,  it  is  not  often  that  chemical  antidotes 
can  be  administered  sufficiently  early  to  prevent  serious  injury. 
Common  chalk  and  calcined  magnesia,  suspended  in  milk,  have 
generally  been  recommended,  and  will  answer  the  purpose  very 
well.  The  alkaline  carbonates,  properly  diluted  with  water  or  milk, 
have  also  been  strongly  advised,  and  are  perhaps  preferable.  In 
the  administration  of  the  alkaline  carbonates,  it  must  be  remem- 
bered that  they  themselves,  in  large  quantities,  are  highly  poisonous. 
Oily  emulsions,  soapsuds,  and  milk  alone  may  be  employed  with 
advantage. 

Several  instances  are  related  in  which  the  timelv  administration 


102  SULPHURIC    ACID. 

of  one  or  other  of  these  antidotes  saved  the  life  of  the  patient,  even 
after  very  large  quantities  of  the  poison  had  been  taken.  The  exhi- 
bition of  the  antidote  should  always  be  followed  by  large  draughts 
of  tepid  water  or  demulcent  fluids,  to  promote  vomiting.  The  whole 
of  the  acid,  however,  may  be  neutralized  and  removed  from  the 
stomach,  and  yet  death  take  place  from  the  effects  of  its  primarv 
action.  On  account  of  this  local  action,  the  patient  is  sometimes 
unable  to  swallow  when  first  seen  by  the  physician.  Under  these 
circumstances  the  poison  may  be  withdrawn  by  means  of  the  stomach- 
pump;  but,  for  obvious  reasons,  this  instrument  should  be  used  with 
great  caution,  and  employed  only  as  a  final  resort. 

Post-mortem  Appearances. — In  poisoning  by  sulphuric  acid, 
the  pathological  appearances  are  more  frequently  peculiar  and  char- 
acteristic than,  perhaps,  in  the  action  of  any  other  poison.  These 
appearances,  however,  will  be  much  modified  by  the  degree  of  con- 
centration of  the  acid,  and  the  length  of  time  the  patient  survived 
after  it  had  been  taken.  In  the  taking  of  the  poison  it  not  unfre- 
quently  happens  that  drops  of  it  become  sprinkled  over  the  face, 
neck,  and  other  portions  of  the  skin ;  in  such  cases,  if  not  very  pro- 
tracted, these  parts  will  present  dark-brown  spots  or  stains.  In  the 
case  cited  above  from  Casper,  in  which  death  took  place  in  an  hour, 
dirty-yellow  parchment-like  streaks,  arising  from  the  trickling  down 
of  the  acid,  extended  from  the  angle  of  the  mouth  to  the  ear ;  similar 
stains  were  present  on  the  arms  and  hands  of  the  child.  The  tongue 
was  white  and  leathery,  and  had  no  acid  reaction.  The  stomach, 
both  externally  and  internally,  was  quite  gray,  and  filled  with  dark, 
bloody,  acid  mucus;  its  tissues  fell  to  pieces  when  touched;  the  vena 
cava  was  moderately  filled  with  a  cherryred  syrupy  and  acid  blood ; 
and  the  liver  and  spleen  were  congested  with  blood  of  the  same  char- 
acter; the  heart  contained  only  a  few  drops  of  blood.  The  tissues 
of  the  oesophagus  were  quite  firm,  and  its  mucous  membrane  had  a 
grayish  color,  and  an  acid  reaction ;  the  larynx  and  trachea  were 
normal. 

In  recent  cases,  the  mucous  membrane  of  the  tongue  and  of  the 
mouth  is  generally  more  or  less  corroded,  and  of  a  white,  but  some- 
times of  a  deep-brown  color;  in  some  instances  large  patches  of  this 
membrane  are  entirely  destroyed.  Similar  appearances  are  usually 
found  in  the  fauces,  and  throughout  the  length  of  the  oesophagus. 
The  lining  membrane  of  this  organ  is  sometimes  much  thickened 


POST-MORTKM    A  I'l'EATlANCES.  103 

and  partially  (Ictaclied.  Instances  are  rocoided,  liowever,  in  whieli 
the  month  and  a'sopliagns  j)resented  but  lew  signs  of  the  local  action 
of  the  poison. 

The  stomach  generally  presents  a  brownish  or  black  ap))earance, 
due  to  the  carbonizing  action  of  the  acid;  its  blood-vessels  are  fre- 
quently much  engorged  with  dark  coagulated  blood,  and  its  tissues 
so  soft  as  to  be  readily  lacerated,  even  by  the  slightest  pressure. 
Sometimes  this  disorganization  is  confined  to  patches,  whilst  in  others 
it  extends  in  the  form  of  lines  or  streaks;  often  the  pylorus  presents 
the  most  decided  marks  of  disorganization.  The  contents  of  the 
stomach  are  usually  thick  and  have  a  brownish  or  charred  appearance 
and  a  highly  acid  reaction.  If  the  stomach  become  perforated,  as 
not  unfrequently  happens,  the  acid  may  escape  and  exert  its  chemical 
action  upon  the  surrounding  organs;  but  this  organ  may  become 
perforated  and  its  contents  not  escape.  The  aperture  of  the  perfora- 
tion usually  presents  a  roundish  appearance,  and.  has  thin,  black, 
irregular  edges.  Sometimes  there  are  several  such  perforations.  In 
one  instance,  the  perforation  measured  about  three  inches  in  diameter, 
and  was  bordered  by  thickened  edges  of  a  dark-brown,  cinder-like 
appearance.  A  few  instances  have  occurred  in  which  there  were  no 
marks  of  the  chemical  action  of  the  poison,  except  in  the  neighbor- 
hood of  the  perforation. 

The  duodenum  and  other  portions  of  the  small  intestines  have 
in  some  instances  presented  signs  of  corrosion  similar  to  those  observed 
in  the  stomach.  Instances  are  reported,  however,  in  which  there  was 
little  or  no  abnormal  change  in  these  organs,  even  when  the  stomach 
was  extensively  disorganized. 

In  making  these  examinations,  the  inspector  should  not  forget 
that  the  action  of  the  acid  may  be  confined  to  the  mouth  and  throat, 
none  of  the  poison  having  passed  into  the  stomach.  In  such  cases, 
as  also  in  others,  the  air-passages  may  be  much  corroded  and  inflamed. 
So,  also,  it  should  be  remembered  that  when  the  acid  is  swallowed 
in  its  diluted  state,  or  the  stomach  contains  much  food  or  liquid,  this 
organ  may  present  simply  signs  of  inflammation,  instead  of  the  dis- 
organized appearances  described  above;  even  when,  however,  the 
acid  is  much  diluted,  the  inside  of  the  stomach  may  present  a  black- 
ened appearance. 

In  the  case  related  by  Mr.  Corfe,  the  epithelium  was  found  de- 
tached or  corruo;ated  from  the  base   of   the   tono-ue   to  the  cardiac 


.104  SULPHURIC   ACID. 

extremity  of  the  stomach.  The  interior  of  the  stomach,  and,  for  six 
inches  below  the  pylorus,  all  the  tissues,  presented  the  appearance  of 
being  covered  with  a  layer  of  black  pitch,  due  to  the  charred  state 
of  the  tissues.  The  ileum  was  also  corroded.  The  blood  in  the  left 
auricle  of  the  heart  was  black  and  clotted ;  the  left  ventricle  was 
empty,  and  rigidly  contracted.  In  the  case  in  which  about  half  an 
ounce  of  the  acid  proved  fatal  to  a  woman  in  about  forty  hours,  the 
mucous  membrane  of  the  cheeks,  gums,  and  tongue  was  not  de- 
stroyed, but  the  epiglottis  was  covered  by  a  thick  layer  of  false 
membrane.  The  lining  membrane  of  the  oesophagus  was  of  a  dirty- 
ash  color,  and  could  readily  be  removed.  The  cardiac  orifice  of  the 
stomach  did  not  show  any  marks  of  the  action  of  the  acid,  but  the 
large  curvature  at  its  cardiac  extremity  presented  several  strong  ridge- 
like elevations;  at  the  pyloric  extremity  of  the  organ  the  action  of 
the  acid  was  less  intense.  The  cavities  of  the  heart  were  empty, 
except  the  right  ventricle,  which  contained  about  half  an  ounce  of 
dark  coagulated  blood. 

In  a  number  of  cases  of  acute  sulphuric  acid  poisoning  examined 
by  Prof.  Casper,  the  hlood  had  in  every  instance  a  cherry-red  color, 
a  more  or  less  ropy  consistency,  and  an  acid  reaction.  He  also  relates 
an  instance  of  similar  poisoning,  in  which  he  found  the  pericardial 
and  amniotic  fluids  of  a  decidedly  acid  reaction,  the  person  poisoned 
being  pregnant.  [Forensic  Medicine,  ii.  58,  83.)  In  the  case  of  another 
pregnant  woman,  quoted  by  Dr.  Beck  [Med.  Jur.,  ii.  475),  the  amni- 
otic fluid,  as  well  as  that  found  in  the  pleura,  peritoneum,  heart,  and 
bladder  of  the  foetus,  had  an  acid  reaction.  It  need  hardly  be 
remarked  that  this  acid  condition  of  the  fluids  of  the  body  would 
be  found  only  in  recent  cases. 

According  to  Casper,  the  bodies  of  persons  poisoned  by  this  acid, 
and  perhaps  by  the  other  mineral  acids,  remain  fresh  and  without 
odor  for  an  unusual  length  of  time.  He  attributes  this  condition  to 
the  free  acid  neutralizing  the  ammonia  evolved  during  the  first  stages 
of  the  process  of  putrefaction. 

When  the  patient  survives  the  primary  effects  of  the  poison  and 
dies  from  secondary  results,  the  appearances  will,  of  course,  differ 
from  those  described  above.  In  such  cases  the  body  is  usually  ex- 
tremely emaciated,  and  one  or  more  portions  of  the  alimentary  canal 
are  much  contracted.  In  Dr.  ¥/ilson's  case,  in  which  life  was  pro- 
tracted for  over  ten  months,  the  upper  third  of  the  oesophagus  shone 


GENERAL  CHEMICAL  NATURE.  105 

like  iui  old  cicatrix,  ami  the  lower  two-tliirds  were  thickened,  nar- 
rowed, and  very  vascular  ;  the  stomach  contained  a  perforation,  which 
was  surrounded  with  softened  edges. 

In  a  case  in  which  a  woman  swallowed  a  quantity  of  strong  sul- 
phuric acid,  but  did  not  die  from  its  effects  until  about  six  weeks 
afterward,  on  inspection  the  mouth  and  fauces  were  found  quite  re- 
covered from  the  effects  of  the  aci<l,  but  there  was  eomi)lete  absence 
of  the  mucous  membrane  of  the  oesophagus.  The  mucous  membrane 
of  the  stomach  was  quite  black  and  partially  detached  at  the  cardiac 
extremity,  and  underneath  it  were  patches  of  fibrinous  exudation  a 
quarter  of  an  inch  thick.     {Half-Yearhj  AbsL,  1872,  108.) 

Chemical  Properties. 

General  Chemical  Nature. — Anhydrous  suljihuric  acid, 
known  also  as  sulphuric  anhydride,  is  a  compound  of  one  atom  of 
Sulphur  with  three  atoms  of  Oxygen,  SO3,  forming  a  white  crystal- 
line substance,  apparently  destitute  of  acid  properties.  It  melts  to 
a  clear  liquid  at  about  18°  C.  (65°  F.),  and  boils  at  about  46°  C. 
(115°  F.),  being  dissipated  in  the  form  of  a  colorless  vapor.  It  has 
an  intense  affinity  for  water,  with  which  it  unites  with  violence, 
forming  the  ordinary  hydrated  acid. 

The  most  concentrated  form  in  which  this  acid  is  found  in  com- 
merce is  usually  a  definite  chemical  combination  of  one  molecule 
of  the  so-called  anhydrous  acid  with  one  molecule  of  water,  H^O, 
803  =  112804.  In  this  state,  when  pure,  it  is  a  colorless,  odorless, 
highly  acrid,  corrosive,  oily  liquid,  having  a  specific  gravity  of  1.845, 
and  containing  81.6  per  cent,  of  the  anhydrous  acid;  it  boils  at  a 
temperature  of  327°  C.  (620°  F.),  and  freezes  at  —34°  C.  (—29°  F.). 
In  certain  respects  this  hydrated  compound  is  the  most  powerful  acid 
known.  It  has  a  strong  attraction  for  water,  which  it  readily  absorbs 
from  the  atmosphere;  it  mixes  with  this  liquid  in  all  proportions, 
with  a  contraction  of  volume,  and  the  evolution  of  much  heat.  In 
proportion  as  it  is  mixed  with  water  it  loses  its  oily  consistency  and 
becomes  specifically  lighter;  when  diluted  to  a  density  of  1.5  its  oily 
appearance  will  have  about  disappeared,  and  it  will  have  a  less  ener- 
getic action  ujDon  organic  substances.  The  density  of  the  diluted 
liquid,  when  pure,  indicates  the  amount  of  real  acid  present. 

The  following  table,  abridged  from  that  first  constructed  by  Dr. 
Ure,  indicates  the  percentage  by  weight  of  anhydrous  (8O3)  and  of 


106 


SULPHURIC   ACID. 


monohydrated  acid  (HgSOJ,  in  pure  solutions  of  different  specific 
gravities : 


STRENGTH    OF    AQUEOUS    SOLUTIONS    OF    SULPHURIC    ACID. 


Peecentage  of 

Peecen 

TAGE   OF 

Peecentage  of 

Spectfic 
Geatity. 

Specific 
Geatitt. 

Specific 
Geavitt. 

S03. 

H2SO4. 

SO3. 

H2SO4. 

SOs. 

H2SO4. 

1.848 

81.54 

100 

1.539 

53.00 

65 

1.218 

24.46 

30 

1.837 

77.46 

95     ; 

1.486 

48.92 

60 

1.179 

20.38 

25 

1.811 

73.39 

90      , 

1.436 

44.85 

55 

1.141 

16.31 

20 

1.767 

69.31 

85    ; 

1.388 

40.77 

50 

I.IOI 

12.23 

15 

1.712 

65.23 

80 

1.344 

36.69 

45 

1.068 

8.15 

10 

1.652 

61.15 

75 

1.299 

32.61 

40 

1.033 

4.08 

5 

1.597 

57.08 

70 

1.257 

28.54 

35 

1.007 

0.81 

1 

The  acid  of  commerce  has  frequently  a  dark-brown  color,  due  to 
its  having  been  brought  in  contact  with  organic  matter.  Sulphuric 
acid  quickly  chars  animal  and  vegetable  substances ;  when  dropped, 
even  in  a  much  diluted  state,  on  black  woollen  cloth,  it  causes  it  to 
assume  a  red  color,  which  after  a  time  fades  to  brown.  Many  sub- 
stances, such  as  certain  metals,  charcoal,  and  various  organic  com- 
pounds, when  heated  with  the  concentrated  acid,  decompose  it  with 
the  evolution  of  sulphurous  acid  gas  (SO2).  In  a  diluted  state,  in 
the  presence  of  some  of  the  metals,  such  as  zinc,  it  decomposes  water, 
at  the  ordinary  temperature,  with  the  evolution  of  hydrogen  gas  and 
the  formation  of  a  salt  of  the  metal. 

The  salts  of  sulphuric  acid  are  usually  colorless,  and  for  the  most 
part  readily  soluble  in  water.  The  sulphates  of  the  fixed  alkalies 
and  of  the  alkaline  earths  are  unchanged  by  a  red  heat,  but  most 
other  sulphates  readily  undergo  decomposition  when  strongly  ignited. 
When  thoroughly  mixed  and  ignited  with  either  charcoal  or  a  mix- 
ture of  carbonate  of  sodium  and  cyanide  of  potassium,  or  with  ferro- 
cyanide  of  potassium,  all  metallic  sulphates  are  readily  decomposed 
with  the  formation  of  a  sulphide  of  the  metal.  This  residue,  when 
acted  upon  by  hydrochloric  acid,  evolves  sulphuretted  hydrogen  gas, 
with  the  formation  of  a  chloride  of  the  metal. 

Special  Chemical  Properties. — When  in  its  concentrated 
state,  sulphuric  acid  may  be  readily  recognized  by  the  properties 
already  mentioned,  such  as  its  carbonizing  action  on  organic  matter, 
evolving  heat  when  mixed  with  water,  etc. ;  but  when  in  a  diluted 


SI'KCIAI.    <IIK.MICAr-    PROPERTIES.  107 

state,  its  presence  lias  to  be  (leleniiiiied  l)y  other  tests.  Tlie  acid  has 
the  property  of  reddening  veratrine,  piperine,  pldoridzine,  oil  of  bitter 
ahnonds,  and  several  other  organic  compounds.  On  account  of  the 
solubility  of  most  of  the  compounds  of  sul{)huric  acid,  there  are  but 
few  reagents  that  precipitate  it  from  solution;  however,  there  is  no 
substiince  that  can  be  detected  with  greater  certainty  and  ease  than 
this  acid. 

The  presence  of  free  sulphuric  acid  in  solution  with  a  sulphate 
may  be  recognized  by  adding  a  little  cane  sugar  and  evaporating  the 
mixture  to  dryness  at  100°  C.  (212°  F.),  when,  if  the  free  acid  be 
present,  the  residue  has  a  black  color,  due  to  the  charring  action  of 
the  acid  ;  if  only  a  trace  of  the  free  acid  be  present,  the  residue  will 
have  a  blackish-green  color.  No  other  free  acid  behaves  in  this 
manner  with  cane  sugar  (Runge). 

In  the  examination  of  the  following  tests,  aqueous  solutions  of 
pure  sulphuric  acid  were  chiefly  employed.  The  fractions  refer  to 
the  amount  of  monohydrated  sulphuric  acid  (HgSOJ  present  in  one 
grain  of  the  solution  ;  and  the  results,  unless  otherwise  stated,  to  the 
behavior  of  one  grain  measure  of  the  solution. 

Chloride  of  Barium. 

Barium  chloride  and  barium  niti'ate  produce  in  solutions  of  free 
sulphuric  acid,  and  of   its  salts,  an  immediate  white  precipitate  of 
barium  sulphate,  BaS04,  which  is  insoluble  in  free  acids  aud  in  the 
caustic  alkalies.     In  applying  this  test  to  neutral  solutions  for  the 
detection  of  combined  sulphuric  acid,  the  solution  should  first  be 
acidulated  with  either  hydrochloric  or  nitric  acid, 
1.  3—-  grain  of   monohydrated  sulphuric  acid   in   solution    in  one 
grain  of   water  yields  with   either  of  the  above    reagents   an 
immediate,  copious  precipitate,  which,  if  the   mixture   be   not 
much  agitated,  consists  of  feathery  stellate  crystals,  needles,  and 
granules,  Plate  IL,  fig.  4.    The  same  crystalline  deposit  may  be 
obtained  from  the  acid  when  in  solution  in  the  form  of  a  sul- 
phate; at  least  from  the  sulphates  of  potassium,  sodium,  mag- 
nesium, and  copper.     If  the  mixture  be  much  agitated  on  the 
addition  of  the  reagent,  the  precipitate  is  wholly  in  the  form 
of  very  small  granules.      The  precipitate,  whether  crystalline 
or  otherwise,  remains   unchanged  on  the  addition  of  several 
drops  of  concentrated  hydrochloric  acid. 


108  SULPHURIC   ACID. 

2.  xoVo   g^^ain  yields  a  rather  copious,  principally  amorphous  but 

partially  granular  precipitate. 

3.  gQ^QQ  grain  :  an  immediate  amorphous  deposit. 

4.  Yo^,VoT  grain  :  after  a  very  little  time  there  is  a  very  good  pre- 

cipitate. A  drop  of  the  sulphuric  acid  solution  immediately 
reddens  litmus-paper. 

5.  25",Wf  grain  :  an   immediate  turbidity,  and,  after  a  little  time, 

a  very  satisfactory  deposit.  A  drop  of  this  solution  faintly 
reddens  litmus-paper. 

6.  5-o,Vo~o   gi^ain :  very  soon  the   mixture   is   distinctly  turbid,  and 

after  several  minutes  it  yields  a  quite  distinct  precipitate. 
This  solution  just  perceptibly  changes  the  color  of  normal 
litmus-paper. 

7.  ___^^^g-^-^  grain :  after  some  minutes  a  distinct  deposit,  which  is 

usually,  especially  when  nitrate  of  barium  is  employed  as  the 
reagent,  granular. 

8.  Yo^.ToT  grain :  in  about  one  minute  there  is  a  perceptible  tur- 

bidity, which  after  several  minutes  becomes  quite  distinct. 

9.  4oo\ToT  gi'ain  yields,  after  from  ten   to  fifteen   minutes,  a  just 

perceptible   cloudiness.      This    result  is  equally  produced  by 

either  of  the  barium  reagents. 
The  last-mentioned  quantity  of  sulphuric  acid  would  form  the 
l-168,000th  of  a  grain  of  barium  sulphate.  It  is  obvious,  there- 
fore, especially  as  there  was  some  fluid  added  with  the  reagent, 
that  this  salt  requires  more  than  168,000  times  its  weight  of  water 
for  solution.  There  has  been  much  discrepancy  among  observers  in 
regard  to  the  limit  of  this  test,  and* the  solubility  of  the  barium  com- 
pound. Thus,  Harting  placed  the  limit  for  chloride  of  barium  at 
one  part  of  anhydrous  sulphuric  acid  in  75,000  parts  of  water ;  while 
Lassaigne  placed  it,  for  nitrate  of  barium,  at  one  part  of  the  acid  in 
200,000  parts  of  water,  after  from  ten  to  fifteen  minutes.  {Gmelin's 
Handbook,  vol.  ii.  177,  192.)  Again,  Gmelin  states  (upon  the 
authority  of  Klaproth  ?)  that  the  sulphate  of  barium  is  soluble  in 
43,000  parts  of  water  {Handbook,  iii.  152);  whereas  Bischof  con- 
cludes from  his  experiments  [Chem.  and  Phys.  GeoL,  i.  450)  that 
this  salt  requires  something  more  than  209,424  times  its  weight  of 
water  for  solution. 

Conju^mation  of  the  Test. —  If  the  sulphate  of  barium  precipitated 
by  this  reagent  be  dried,  then  thoroughly  mixed  with  about  twice 


SPECIAL   CHEMICAL    PROPERTIES. 


109 


its  weight  of  powdered  cliarcoal  or  of  :i  well-ilritil  mixture  of  equal 
parts  of  sodiiiin  carbonate  and  potassium  cyanide,  and  the  mixture 
lieated  to  redness,  for  convenience  on  })latinnm-foil,  the  barium  salt 
yields  up  its  oxygen  and  becomes  reduced  to  sulpliide  of  barium 
(BaS).  This  same  conversion  may  be  effected  in  a  similar  manner 
by  ferrocyanide  of  potassium,  as  first  advised  by  Dr.  E.  Davy  for 
the  reduction  of  arsenical  compounds;  the  salt  should  be  previously 
pulverized  and  thoroughly  dried  at  100°  C.  (212°  F.)  in  a  water-bath. 
Before  using  cither  of  these  reducing  agents  for  the  reduction  of  the 
barium  precipitate,  a  portion  of  the  agent  should  be  ignited  alone, 
and  then  tested  for  a  sulphide,  in  the  manner  about  to  be  described : 
this  precaution  is  necessary,  since  the  reducing  agent  itself  might 
contain  a  sulphate.  In  the  absence  of  platinum-foil  or  a  small 
platinum  or  porcelain  crucible,  the  ignition  of  the  sulphate  mixture 
may  be  performed  in  an  ordinary  reduction-tube. 

The  presence  of  a  sulphide  in  the  ignited  sulphate  mixture  may 
be  shown  by  moistening  the  cooled  residue  with  diluted  hydrochloric 
acid,  when  it  will  evolve  sulphuretted  hydrogen  gas.  The  presence 
of  this  gas  may  be  recognized  by  its  peculiar  odor,  and  by  its  impart- 
ing a  brown  color  to  a  slip  of  bibulous  paper  previously  moistened 
with  a  solution  of  acetate  of  lead  and  exposed  to  it.  Or,  the  evolved 
gas  may  be  conducted  into  a  solution  of  acetate  of  lead,  when  it  will 
produce  a  black  precipitate  of  lead  sulphide,  or  at  least  impart  a 
brown  coloration  to  the  solution.  For  this  purpose, 
the  cooled  residue  is  placed,  with  a  few  drops  of 
w'ater,  in  a  small  test-tube.  Fig.  1,  A,  and  treated 
with  a  few  drops  of  hydrochloric  acid,  added  by 
means  of  a  small  funnel-tube,  a;  the  evolved  gas 
is  conducted  through  a  delivery-tube,  6,  into  a  few 
drops  of  the  lead  solution,  acidulated  with  acetic 
acid,  contained  in  a  second  test-tube,  B.  By  blow- 
ing through  the  funnel-tube  of  the  apparatus,  the 
last  traces  of  the  evolved  gas  will  be  brought  in 
contact  with  the  lead  solution.  By  this  method, 
the  sulphuretted  hydrogen  evolved  from  the  1-lOOth  of  a  grain  of 
sulphuric  acid  will  produce  a  distinct  precipitate,  and  from  the 
1-lOOOth  of  a  grain,  a  distinctly  brown  coloration. 

So,  also,  the  ignited  residue  may  be  placed  on  a  piece  of  paper 
which  has  previously  been  saturated  with  a  lead  solution  and  nearly 


Apparatus  for  detection  of 
sulphide  of  barium. 


110  SULPHURIC    ACID. 

dried,  and  then  touched  with  a  drop  of  diluted  hydrochloric  acid, 
when  the  moistened  paper  will  assume  a  brown  color;  or,  it  may- 
be placed  in  a  watch-glass  and  moistened  with  the  acid,  and  another 
similar  glass,  containing  a  fragment  of  paper  moistened  with  the 
lead  solution,  inverted  over  this.  By  either  of  these  methods,  espe- 
cially the  latter,  the  mofet  minute  traces  of  a  sulphide  will  manifest 
themselves. 

Fallacies. — Solutions  of  salts  of  barium  also  produce  white  pre- 
cipitates in  solutions  of  Selenie  and  Hydrofluosilieie  acids,  even  in  the 
presence  of  other  free  acids.  Both  these  substances  are  very  rare, 
and  only  possible  to  be  met  with  in  medico-legal  investigations.  The 
fluorine  precipitate,  at  least  from  strong  solutions,  is  crystalline;  but 
the  form  of  the  deposit,  Plate  II.,  fig.  4,  readily  distinguishes  it  from 
the  sulphate  precipitate.  The  selenate  of  barium  is  amorphous. 
This  salt  is  soluble  in  hot  hydrochloric  acid,  with  the  evolution  of 
free  chlorine;  but  the  silico-fluoride  of  barium  is  almost  wholly 
insoluble  in  either  hydrochloric  or  nitric  acid.  Solutions  of  selenie 
acid,  like  those  of  sulphuric  acid,  yield  precipitates  when  treated  with 
soluble  salts  of  strontium  and  of  lead;  but  the  fluorine  acid  forms 
no  precipitate  with  solutions  of  these  metals.  The  precipitate  from 
either  of  these  acids  would  not,  of  course,  yield  a  sulphide  upon 
ignition  with  a  reducing  agent. 

In  applying  this  test  it  must  also  be  borne  in  mind  that  when 
relatively  large  quantities  of  strong  solutions  of  chloride  of  barium, 
and  of  barium  nitrate,  are  added  to  a  liquid  containing  much  free 
hydrochloric  acid  or  free  nitric  acid,  it  may  yield  a  white  precipitate 
of  the  reagent  salt,  since  these  salts  are  less  soluble  in  a  strong 
solution  of  either  of  these  acids  than  in  pure  water.  Under  these 
circumstances,  however,  the  precipitate  would  readily  disappear  on 
the  addition  of  water ;  whereby  it  would  be  distinguished  from  the 
barium  sulphate. 

When  the  reagent  is  added  to  neutral  or  alkaline  solutions,  it  pro- 
duces white  precipitates  with  several  acids  other  than  those  already 
mentioned,  such  as  carbonic,  phosphoric,  oxalic,  etc. ;  but  the  precipi- 
tate produced  from  either  of  these,  unlike  the  sulphate  of  barium,  is 
readily  soluble  in  hydrochloric  and  nitric  acids. 

2.  Nitrate  of  Strontium. 
This  reagent  produces  in  solutions  of  free  sulphuric  acid,  and  of 


SPECIAL   CHEMICAL    I'Kol'ERTIP-S.  Ill 

its  salts,  11  wliite  precipitate  of  strontium  sulphate,  SrSO^,  wiiich  is 
quite  |)crceptibly  soluble  in  hydrochloric  and  nitric  acids,  and  much 
more  soluble  in  water  than  the  corresponding  barium  compound. 
From  dilute  solutions  the  formation  of  the  precipitate  is  much 
])romoted  by  warming  the  mixture,  and  also  by  agitating  it  with  a 
glass  rod. 

If  the  i)recipitate  be  collected  and  ignited  with  charcoal,  or  any 
other  reducing  agent,  it  leaves  a  residue  of  sulphide  of  strontium, 
which  may  be  recognized  as  such  in  the  same  manner  as  the  sulphide 
of  barium. 

1.  yi-j  grain  of  free  sulphuric  acid,  in  one  grain  of  water,  yields 

with  the  reagent  a  rather  copious  crystalline  precipitate,  consist- 
ing of  groups  of  exceedingly  delicate  transparent  needles,  and 
granules,  Plate  II.,  fig.  6.  The  granules  are  somewhat  larger 
than  those  produced  by  the  barium  reagent.  The  deposit  re- 
mains unchanged  on  the  addition  of  a  few  drops  of  hydrochloric 
acid.  Similar  results  are  obtained  from  the  acid  when  in  solu- 
tion in  the  form  of  a  sulphate. 

2.  -j-j5\nr  grain  :  au  immediate  cloudiness,  and  very  soon  a  quite  good 

granular  deposit. 

3.  -g-yVir  g'^'ain  :  in  about  one  minute  there  is  a  perceptible  cloudiness, 

and  in  a  few  minutes  a  good  granular  precipitate. 

4.  xo^.Vinr  grain :  after  a  few  minutes  a  distinct  turbidity,  and  after 

several  minutes  a  quite  satisfactory  deposit.  The  separation  of 
the  precipitate  is  much  hastened  by  agitating  the  mixture. 

5.  2T.W0  gi'aiu,  yields  after  several  minutes  a  just  perceptible  cloudi- 

ness, which  increases  but  little,  even  after  half  an  hour. 

"Wackenroder  states  that  the  sulphate  of  strontium  dissolves 
slowly  but  completely  in  a  solution  of  common  salt,  in  which  respect 
it  differs  from  the  corresponding  salt  of  barium. 

The  reaction  of  this  test  is  subject  to  about  the  same  fallaeies  as 
the  preceding  reagent. 

3.  Acetate  of  Lead. 

Solutions  of  free  sulphuric  acid  and  of  sulphates  yield  with  this 
reagent  a  white  amorphous  precipitate  of  sulphate  of  lead,  PbSO^, 
which  is  sparingly  soluble  in  dilute  hydrochloric  and  nitric  acids. 
It  is  somewhat  soluble  jn  solutions  of  the  caustic  alkalies,  as  also  in 
some  of  the  salts  of  ammonia. 


112  SULPHURIC   ACID. 

1.  -j^  grain   of  the  acid  yields  a  copious   amorphous   precipitate, 

which  in  a  large  measure  is  dissolved  on  the  addition  of  a  single 
drop  of  concentrated  hydrochloric  acid. 

2.  YoVo  g™"  •  ^  rather  copious  precipitate,  which,  on  the  addition 

of  a  drop  of  hydrochloric  acid,  very  nearly  all  disappears. 

3.  xF.VoT  grain  yields  an  immediate  turbidity,  and  in  a  few  minutes 

a  very  satisfactory  deposit. 

4.  YF-VoT  g™ii  •   after    some    minutes  a  just  perceptible  turbidity, 

which  increases  but  little  on  standing. 
This  test  is  subject  to  many  more  fallacies  than  either  of  the  tests 
already  mentioned. 

4.    Ver citrine. 

Veratrine,  when  added  to  a  drop  of  concentrated  sulphuric  acid, 
slowly  assumes  a  yellow  color  and  in  a  little  time  dissolves  to  a 
beautiful  crimson-red  solution.  This  solution  is  produced  imme- 
diately by  warming  the  mixture.  In  the  diluted  acid,  the  alkaloid 
dissolves  slowly  without  change  of  color. 

1.  yi-Q^  grain  :  when  a  small  quantity  of  the  alkaloid  is  introduced 

into  one  grain  of  a  1-1 00th  solution  of  the  free  acid  and  heat 
applied,  it  dissolves  to  a  colorless  mixture,  which,  when  evapo- 
rated to  dryness  on  a  water-bath,  leaves  a  beautiful  crimson- 
colored  deposit. 

2.  -YooT  gi'ain  of  the  acid,  when  treated  in  a  similar  manner,  leaves 

a  residue,  the  border  of  which  has  a  fine  crimson  color. 

3.  s-qVo    gi'ain  :  the  residue  has  a  just  perceptible  red  tint,  which, 

however,  is  not  well  marked. 

Since  this  reagent  produces  no  coloration  with  neutral  sulphates, 
it  serves  to  distinguish  the  uncombined  acid  from  these  salts.  And 
for  this  purpose  we  recommend  it  as  much  superior  in  every  respect 
to  the  cane-sugar  method  of  Kunge.  A  drop  of  a  saturated  solution 
of  the  neutral  sulphate  of  either  of  the  fixed  alkalies  and  of  other 
similar  salts,  when  treated  with  the  alkaloid  and  evaporated  to  dry- 
ness, failed  to  produce  any  red  coloration  whatever. 

This  reaction  is  peculiar  to  the  acid  in  question. 

Other  Reactions. — Chloride  of  Calcium  produces  in  somewhat 
concentrated  solutions  of  free  sulphuric  acid  and  of  its  salts  a  white, 
granular,  but  sometimes  crystalline,  precipitate  of  calcium  sulphate, 
which  slowly  disappears  on  the  addition  of  water,  it  being  rather 


SEPARATION    I'KoM    ollOAXIC    MIXTURES.  113 

freely  soluble  in  this  llnid.     ( )iic  i^naiii  of  a  1-lOOtli  solution  of  the 
free  acid  yiehls  only  a  slight  tiirhidity, 

3fcfa//ic  copper,  when  present  in  stron<j,  i)oilin(r  solntions  of 
sulphnric  acid,  deconij)oscs  it,  with  the  evolution  of  sulphurous 
acid  jjas  (SOo),  w  Inch  may  be  recognized  by  its  peculiar  odor  and  its 
bleaching  jiroperties.  This  dcconij)osition,  however,  does  not  occur 
when  the  acid  is  diluted  with  as  much  as  about  ten  times  its  weight 
of  water.  So,  also,  when  not  too  dilute,  the  acid  decomposes,  at  ordi- 
nary temperatures,  the  sulphide  of  iron,  with  the  evolution  of  sul- 
phuretted hydrogen  gas,  known  by  its  peculiar  odor  and  its  action 
on  salts  of  lead.  When  the  acid  contains  about  twenty-five  times 
its  weight  of  water,  the  decomposition  takes  place  very  slowly;  and 
when  but  little  more  diluted,  not  at  all.  This  decomposition,  how- 
ever, is  common  to  several  other  acids. 

Sepaeatiox  from  Oegaxic  Mixtures. 

Suspected  Solutions. — If  the  solution  presented  for  examination 
be  some  article  of  drink,  food,  or  medicine  having  a  strong  acid  reac- 
tion, and  free  from  mechanically  suspended  matter  or  solids,  the  tests 
for  sulphuric  acid  may  be  applied  at  once,  even  though  the  liquid  be 
highly  colored.  For  this  purpose,  a  given  portion  of  the  solution, 
after  concentration  if  necessary,  is  treated  with  a  solution  of  chloride 
of  barium  as  long  as  it  produces  a  precipitate.  The  mixture  is  then 
warmed,  and  the  deposit  collected  on  a  filter,  well  washed  with  water 
containing  pure  hydrochloric  acid,  and  dried.  If  the  mixture  con- 
taining the  precipitate  be  so  strongly  acid  that  it  perforates  the  filter, 
the  latter  is  supported  on  a  muslin  cloth,  or  the  solution  is  diluted 
before  filtration. 

When  an  organic  mixture  thus  yields  with  chloride  of  barium  a 
white  precipitate  which  is  insoluble  in  hydrochloric  acid,  there  is 
scarcely  a  doubt  of  the  presence  of  sulphuric  acid,  either  free  or 
otherwise.  It  is  more  satisfactory,  however,  to  ignite  a  portion  of 
the  dried  precipitate  with  a  reducing  agent  and  determine  the  pres- 
ence of  a  sulphide  in  the  residue,  in  the  manner  already  pointed  out. 
When  this  examination  yields  positive  results,  there  is  no  longer  any 
doubt  whatever  of  the  presence  of  the  acid.  The  reactions  of  this 
test  may,  however,  be  confirmed  by  examining  other  portions  of  the 
solution  bv  some  of  the  other  tests  for  the  acid. 


114  SULPHURIC   ACID. 

If  the  mixture  presented  for  examination  contains  much  solid 
organic  matter,  it  should,  after  dilution  if  necessary,  be  kept  at  a 
boiling  temperature  for  ten  or  fifteen  minutes,  then,  when  cooled, 
filtered,  and  the  solids  on  the  filter  well  washed  with  warm  water. 
The  filtrate  thus  obtained  is  properly  concentrated  and  examined  in 
the  manner  just  described. 

Although  in  this  manner  the  presence  of  sulphuric  acid  may  be 
fully  and  unequivocally  established,  yet  it  does  not  follow  that  it  was 
present  in  its  free  state,  even  when  the  liquid  had  a  strong  acid  reac- 
tion. For  it  may  have  existed  in  the  form  of  one  of  the  acid  sul- 
phates, such  as  common  alum,  the  solutions  of  which  have  an  acid 
reaction ;  or  it  may  have  been  present  as  a  neutral  sulphate,  such  as 
sulphate  of  magnesium,  and  the  acidity  of  the  mixture  have  been 
due  to  the  presence  of  some  other  acid,  as  acetic  acid  in  the  form  of 
vinegar ;  or,  lastly,  only-  a  portion  of  it  may  have  been  free,  the 
mixture  having  contained  both  the  free  acid  and  a  sulphate. 

To  determine  this  point,  a  portion  of  the  suspected  solution  is 
evaporated  to  dryness,  when,  if  it  leaves  no  saline  residue  or  only  an 
insignificant  one,  it  is  certain  that  the  acid  existed  in  its  free  state : 
if,  however,  it  leaves  a  saline  deposit,  then  there  may  have  been  no 
free  sulphuric  acid  present.  When  the  original  mixture  contains 
much  organic  matter,  it  may  be  difficult  at  first,  by  simple  inspection, 
to  determine  the  presence  or  otherwise  of  saline  matter  in  the  evap- 
orated residue.  When  this  is  the  case,  the  residue  should  be  moist- 
ened with  pure  nitric  acid  and  the  mixture  evaporated  at  a  moderate 
heat  to  dryness,  and  the  operation  repeated  until  the  dry  residue  has 
a  yellow  color,  after  which  the  heat  is  gradually  increased  till  the 
organic  matter  is  entirely  destroyed,  when,  if  a  salt  be  present,  it  will 
remain  as  a  white  mass.  The  nitric  acid  in  this  operation  facilitates 
the  decomposition  of  the  organic  matter,  and  at  the  same  time  pre- 
vents the  reduction  of  any  sulphate  present  to  the  state  of  sulphide, 
which  might  otherwise  take  place  during  the  oxidation  of  the  organic 
matter.  If  the  ignited  mixture  thus  leaves  a  saline  residue,  a  portion 
or  the  whole  of  the  sulphuric  acid  may  have  existed  in  the  form  of 
a  sulphate.  A  portion  of  the  residue  may  be  dissolved  in  water  and 
the  solution  tested  in  the  ordinary  manner.  It  does  not  follow,  how- 
ever, from  thus  obtaining  a  sulphate,  for  reasons  pointed  out  here- 
after, that  even,  any  part  of  the  acid  originally  existed  in  its  com- 
bined state;  yet,  under  these  circumstances,  it  can  never  be  proved 


SEPARATION    FUO.M    ORGANIC    MIXTURES.  115 

by  clieinical  inuaiis  that  the  whole  ot"  the  acid  was  originally  present 
in  its  free  state. 

For  determininej  and  se])aratinL!;  free  snlphnric  aeid  from  solutions 
of  its  salts  various  methods  have  been  advised.  Thus,  it  has  been 
projiosed  to  concentrate  the  mixture  to  near  dryness  and  agitate  the 
residue  with  absolute  alcohol  or  ether,  for  the  purpose  of  dissolving 
the  free  acid  while  its  salts  would  remain  insoluble.  But,  as  remarked 
by  Dr.  Christison,  alcohol  will  extract  a  portion  of  sulphuric  acid 
from  acid  sulphates,  and  even  neutral  sulphates  are  not  wholly  insol- 
uble in  this  menstruum  ;  and  again,  ether  extracts  the  free  acid  only 
to  a  very  limited  extent,  even  in  the  presence  of  only  a  very  minute 
quantity  of  water.  It  has  also  been  proposed  to  add  to  the  warmed 
mixture  finely-powdered  barium  carbonate,  in  small  quantity  at  a 
time,  as  long  as  it  produces  effervescence,  by  which  the  free  acid 
would  be  precipitated  as  barium  sulphate,  while  the  soluble  sulphate 
present  would  remain  unacted  upon.  The  precipitate  thus  obtained 
would,  therefore,  represent  the  amount  of  free  acid  present.  By 
stopping  the  addition  of  the  barium  carbonate  the  moment  efferves- 
cence ceases,  this  method,  under  certain  conditions,  yields  very  ac- 
curate results;  yet,  if  the  sulphate  present  was  a  neutral  alkaline 
salt,  it  would,  partially  at  least,  be  estimated  as  an  acid  sulphate, 
while,  on  the  other  hand,  some  of  the  acid  sulphates,  as  common 
alum,  decompose  carbonate  of  barium  with  effervescence.  Should, 
however,  the  original  mixture  contain  a  sulphate  and  a  free  acid 
not  sulphuric,  the  operator  might  be  wholly  misled  by  this  method. 
Thus,  if  the  free  acid  existed  in  excess  over  the  salt,  the  carbonate 
of  barium  would  precipitate  the  whole  of  the  sulphuric  acid  from 
the  salt,  and  still  give  rise  to  effervescence :  under  these  circum- 
stances, therefore,  the  whole  of  the  precipitate  would  be  due  simply 
to  the  presence  of  a  sulphate. 

When  the  examination  has  shown  the  presence  of  sulphuric  acid 
in  a  solution  which  contains  a  saline  compound,  the  safest  and  most 
accurate  method  for  determining  whether  or  not  the  whole  of  the 
acid  may  have  existed  in  the  form  of  a  sulphate  is  the  following : 
A  given  volume  of  the  solution,  after  the  addition  of  a  little  hydro- 
chloric acid,  is  treated  with  excess  of  chloride  of  barium,  and  the 
precipitate  collected,  dried  and  weighed,  in  the  manner  described 
hereafter;  an  equal  volume  of  the  solution  is  then  evaporated  to 
dryness,  the  residue  thoroughly  dried,  but  not  ignited,  then  dissolved 


116  StTLPHURIC   ACID. 

in  acidulated  water,  the  filtered  solution  precipitated  as  before,  and 
the  dried  deposit  weighed.  Every  2.38  parts  by  weight  of  the 
former  precipitate  in  excess  over  the  latter  correspond  to  one  part 
of  free  monohydrated  sulphuric  acid.  This  estimate  mav,  however, 
fall  short  of  the  real  amount  of  the  free  acid  originally  present,  but 
it  could  never  exceed  it.  If,  in  determining  the  amount  of  combined 
acid  in  the  evaporated  residue,  the  latter  be  ignited,  any  acid  sul- 
phate present  might  give  up  a  portion  of  its  acid,  which  would, 
therefore,  be  estimated  as  free;  so,  also,  the  ignition  might  reduce 
some  of  the  sulphate  to  the  state  of  sulphide,  and  thus  cause  an 
error  in  the  same  direction.  If  the  suspected  solution  contained 
simply  a  sulphate  and  a  free  acid  other  than  sulphuric,  the  precipi- 
tates obtained  by  both  of  the  above  operations  would,  of  course,  be 
equal  in  weight. 

Although  this  method,  as  just  intimated,  may,  under  certain  con- 
ditions, fail  to  show  the  whole  of  the  acid  as  free  that  really  existed 
as  such,  yet  in  most  instances  this  would  not  be  likely  to  affect  seri- 
ously the  results.  Nevertheless,  cases  might  occur  in  which  the  op- 
erator would  be  led  to  conclude  that  little  or  even  none  of  the  acid 
was  present  in  its  free  state,  when  the  whole  of  it  had  been  added  as 
such.  Thus,  for  example,  if  free  sulphuric  acid  was  added  to  a  solu- 
tion of  chloride  of  sodium,  or  common  salt,  the  mixture  on  evapora- 
tion would  leave  an  acid  sulphate  of  sodium,  the  chlorine,  in  part  at 
least,  of  the  common  salt  being  expelled  in  the  form  of  hydrochloric 
acid.  If,  under  these  circumstances,  the  amount  of  salt  present 
equalled  or  exceeded  the  acid  added,  the  whole  of  the  latter  would 
be  estimated  as  combined.  Similar  results  would  be  observed  in 
regard  to  solutions  of  other  salts.  In  a  solution  containino^  one  base 
and  two  different  acids,  especially  in  about  equivalent  proportions,  it 
is  impossible  by  chemistry  alone  to  determine  which  acid  originally 
existed  in  combination  with  the  base.  Cases  of  this  kind,  it  is  true, 
are  not  likely  to  occur  in  medico-legal  investigations,  especially  in 
the  examination  of  suspected  articles  of  food  or  drink,  vet  it  is  well 
to  bear  in  mind  the  possibility  of  their  occurrence.  In  suspected  solu- 
tions containing  this  poison,  the  nature  of  the  mixture  and  attending 
circumstances  usually  leave  no  doubt  as  to  its  true  character. 

Contents  of  the  Stomach. — These,  carefully  collected  in  a  large 
porcelain  dish,  are  tested  in  regard  to  their  chemical  reaction,  any 
solids  present  cut  into  small  pieces,  and  the  mixture,  after  the  addition 


SEPARATION  FROM  ORGANIC  MIXTURES.         117 

of  water  it'  necessary,  kept  at  about  a  boiling  temperature  for  half 
an.  honr  or  Ioniser;  tJu;  cooled  niiiss  is  then  strained,  the  solids  wasjied 
with  hot  water,  the  united  licjnids  concenti'ateil,  filtered,  and  the  fil- 
trate examined  in  tlu;  manner  pointed  out  ai)ove.  This  method 
would,  of  course,  be  e([ually  a|)plicable  for  the  examination  of  the 
matters  ejected  from  the  stomach  by  vomitintr  during  life.  Should 
an  antidote,  sucli  as  an  alkaline  carbonate,  have  been  administered, 
the  contents  of  the  stomach,  as  well  as  the  matters  vomited,  may 
contain  the  acid  only  in  the  form  of  a  sulphate  and  have  a  neutral 
reaction.  Under  these  circumstances,  in  the  pre[)aration  of  the  mix- 
ture, it  should  be  strongly  acidulated  with  hydrochloric  acid ;  the 
amount  of  combined  sulphuric  acid  is  then  estimated  in  the  manner 
already  described. 

So,  also,  if  the  person  had  been  actively  treated  or  survived  the 
taking  of  the  poison  some  days,  it  may  have  entirely  disappeared  from 
the  stomach.  This  result  has  been  observed  in  several  instances  in 
which  death  took  place  within  even  short  periods.  Thus,  in  a  case 
mentioned  by  Mertzdorif,  in  which  the  acid  proved  fatal  within 
twelve  hours  to  a  child,  the  contents  of  the  stomach  had  no  acid 
reaction,  but,  on  the  contrary,  an  ammoniacal  odor,  and  contained  a 
soluble  sulphate,  probably  the  sulphate  of  ammonium.  {Christison 
On  Poisons,  126.)  This  conversion,  according  to  Orfila,  always 
takes  place  with  greater  or  less  rapidity  when  the  acid  is  present  in 
decomposing  nitrogenized  organic  mixtures.  M.  Buchner  mentions 
five  instances  of  fatal  poisoning  by  this  acid  and  nitric  acid,  in  M-hich 
there  was  a  failure  to  detect  the  presence  of  the  acid  after  death. 
[Jour.  Chim.  Med.,  1867,  179.) 

It  is  well  known  that  the  natural  secretions  of  the  stomach  have 
usually  a  distinctly  acid  reaction,  due  to  the  presence  of  minute 
quantities  of  hydrochloric  and  lactic  acids.  Whether  the  acidity  of 
the  mixture  under  examination  is  due  simply  to  these  acids  or  really 
to  the  presence  of  free  sulphuric  acid,  can,  of  course,  be  determined 
only  by  the  attending  circumstances  and  a  chemical  analysis.  In 
determining  the  quantity  of  free  sulphuric  acid  present,  it  must  be 
borne  in  mind  that  the  contents  of  the  stomach  usually  contain  small 
quantities  of  alkaline  salts,  particularly  chlorides,  and  that  these,  on 
evaporating  the  mixture  to  dryness,  wnll  convert  a  corresponding 
portion  of  the  free  acid  into  sulphates  :  the  proportion  thus  converted, 
however,  would  rarely  affect  the  general  results.     In  this  connection 


118  SULPHURIC    ACID. 

it  must  also  be  remembered  that  sulphates  may  be  normally  present 
in  very  minute  quantity  in  articles  of  food  and  complex  organic  mix- 
tures; and,  moreover,  that  some  of  these  salts  are  used  medicinally 
in  large  doses. 

From  the  above  considerations,  it  is  evident  that  in  poisoning  by 
sulphuric  acid  cases  may  readily  arise  in  which  the  proof  of  the 
poisoning  will  rest  chiefly  or  entirely  upon  the  symptoms  and  post- 
mortem appearances.  In  all  such  cases,  however,  we  should  be  able 
to  account  satisfactorily  for  the  failure  of  the  chemical  analysis. 

Fj'om  organiG  fabrics. — The  texture  of  articles  of  clothing  with 
which  sulphuric  acid  comes  in  contact  is  usually  more  or  less  de- 
stroyed, and  the  spots  remain  moist  for  a  long  period,  due  to  the 
affinity  of  the  acid  for  water;  so,  also,  the  color  of  the  article  is 
more  or  less  changed,  it  in  most  instances  assuming  a  reddish  or 
brownish  hue.  These  spots  may  retain  an  acid  reaction  for  many 
months  or  even  years. 

The  presence  of  the  acid  in  stains  of  this  kind  may  be  deter- 
mined by  boiling  the  stained  portion  with  a  small  quantity  of  pure 
w^ater,  filtering  the  solution  thus  obtained,  and  examining  the  filtrate 
in  regard  to  its  chemical  reaction  and  with  chloride  of  barium,  in  the 
usual  manner.  A  portion  of  the  filtrate  should  also  be  examined 
in  regard  to  the  presence  of  saline  matter.  Should  the  latter  be 
present  with  the  acid,  it  then  becomes  necessary  to  determine,  in  the 
manner  already  indicated,  whether  or  not  the  whole  of  the  acid  may 
have  been  in  its  combined  state.  If  the  examination  shows  that 
this  may  have  been  the  case,  it  is  then  necessary  to  examine  an  equal 
portion  of  the  unstained  article,  after  the  same  process,  since  in  the 
preparation  of  fabrics  of  this  kind  minute  quantities  of  sulphates 
are  sometimes  employed. 

Quantitative  Analysis. — Sulphuric  acid  is  usually  estimated 
in  the  form  of  sulphate  of  barium.  For  this  purpose  the  solution 
is  treated  with  slight  excess  of  chloride  of  barium,  and  the  mixture 
gently  heated  until  the  barium  precipitate  has  completely  subsided. 
The  deposit  is  then  collected  on  a  small  filter  of  known  ash, 
repeatedly  washed  with  hot  water  containing  hydrochloric  acid, 
dried,  ignited,  and  weighed.  When  only  a  small  quantity  of  the 
precipitate  is  present,  after  being  washed  and  dried  it  should  as  far 
as  practicable  be  removed  from  the  filter   and   ignited  alone ;  the 


NITRIC    ACID.  119 

filtor  with  any  adlicrcnt  sulphate  is  then  ignited,  and  the  weight  of 
the  residue,  after  (k"(hictiii^  the  ash  of  tiie  filter,  added  to  the  weiglit 
of  the  previously  ignited  sulphate. 

Every  one  hundred  parts  by  weiglit  of  barium  sulphate  thus 
obtained  correspond  to  42.06  parts  of  monohydrated  sulphuric  acid, 
105  o-rains  of  which  measure  one  fluid-drachm. 

Section  II. — Nitric  Acid. 

Nitric  Acid,  or  aquafortis,  as  found  in  the  shops,  is  a  powerfully 
corrosive  acid  liquid,  having  usually  a  more  or  less  yellow  or  even 
reddish  color.  In  its  action  upon  organic  substances  it  is  about 
equally  active  with  sulphuric  acid.  Instances  of  poisoning  by  it, 
however,  have  been  of  very  much  less  frequent  occurrence  than  by 
the  latter. 

Symptoms. — These  in  most  respects  are  identical  in  kind  with 
those  observed  in  sulphuric  acid  poisoning.  Wlien  the  acid  is  swal- 
lowed in  its  concentrated  state,  the  mucous  membrane  of  the  mouth 
and  other  parts  with  which  the  liquid  comes  in  contact  is  imme- 
diatelv  corroded  and  assumes  a  white  appearance,  which,  however, 
unlike  that  produced  by  sulphuric  acid,  soon  changes  to  yellow,  and 
then  in  some  instances  slowly  becomes  more  or  less  brown.  All 
spots  produced  on  the  external  skin  by  the  acid  very  soon  acquire  a 
permanent  yellow'  color. 

The  usual  symptoms  are  violent  pain  in  the  mouth,  oesophagus, 
and  stomach;  copious  eructations  of  gaseous  matter,  having  some- 
times a  reddish  color,  due  to  the  presence  of  the  decomposed  acid; 
excessive  vomiting  of  strongly  acid,  yellow  or  brownish  matters ; 
tenderness  and  tension  of  the  abdomen ;  general  coldness  of  the  body, 
especially  in  the  extremities;  difficulty  of  respiration  and  of  deglu- 
tition, from  the  local  action  of  the  acid  on  the  internal  organs  of 
the  mouth  and  fauces;  a  small  and  frequent  pulse;  extreme  thirst, 
cold  sweats,  and  great  prostration  of  strength.  The  local  action  of 
the  acid  may  be  confined  to  the  mouth  and  fauces,  none  of  the  poison 
having  been  swallowed. 

In  most  instances  the  more  immediate  symptoms  produced  by 
nitric  acid  are  proportionate  to  the  degree  of  its  concentration  and 
the  quantity  taken  ;  but  this  is  by  no  means  always  the  case.  Thus, 
Dr.  Beck  cites  the  case  of  a  young  man  who  died  in  twenty  hours, 
from  the  effects  of  the  acid,  without  at  any  time  showing  signs  of 


120  NITRIC   ACID. 

acute  pain  or  of  agitation ;  yet  after  death  there  was  found  perfo- 
ration of  the  stomach,  with  great  effusion  of  its  contents  into  the 
abdomen.  In  another  case,  a  woman  swallowed  a  quantity  of  the 
poison,  and,  at  least  for  some  hours  afterward,  there  was  neither  agi- 
tation, pain,  nor  vomiting,  but  a  condition  rather  indicating  typhus 
fever.  She  died  the  following  day,  and  on  examination  of  the  body 
there  was  found  most  extensive  disorganization  of  the  abdominal 
organs :  perforation  of  the  stomach,  gangrenous  spots,  effusion  into 
the  abdomen,  marked  erosion,  and  a  general  yellow  color  of  all  the 
viscera. 

In  a  case  reported  by  Dr.  Stevenson  [G-uy^s  Hosp.  Rep.,  1872, 
223),  a  man,  aged  twenty-one,  swallowed  with  suicidal  intent  three 
fluid-ounces  of  nitric  acid,  of  the  ordinary  strong  commercial  prep- 
aration. Although  magnesia  was  given  as  an  antidote,  the  man  died 
seventeen  hours  after  taking  the  poison,  after  the  ordinary  symptoms 
of  poisoning  by  the  mineral  acids,  but  he  suffered  much  less  pain 
during  the  last  few  hours  of  life  than  during  the  period  more 
immediately  following  the  taking  of  the  acid. 

If  the  patient  survive  the  primary  effects  of  the  poison,  these 
may  be  succeeded  by  irregular  fever,  obscure  pains  in  the  throat  and 
epigastric  region,  impaired  digestion,  irritability  of  the  stomach,  fre- 
quent vomiting,  obstinate  constipation,  dryness  of  the  skin,  disturbed 
respiration  and  deglutition,  sometimes  profuse  salivation,  fetid  breath, 
frequent  rigors,  and  great  muscular  emaciation.  Sometimes  large 
membranous  flakes,  or  even  masses  of  the  lining  membrane  of  the 
throat  and  oesophagus,  are  ejected  with  the  vomited  matters. 

The  vapor,  or  fumes,  arising  from  nitric  acid  has  in  several  in- 
stances caused  death.  In  an  instance  of  this  kind,  a  chemist,  Mr. 
Stewart,  of  Edinburgh,  and  his  assistant  inhaled  the  fumes  while 
endeavoring  to  save  a  portion  of  the  liquid  that  had  escaped  from 
a  broken  jar.  After  an  hour  or  two,  the  former  began  to  experi- 
ence difficulty  of  breathing,  and  sent  for  medical  advice,  but  he  very 
rapidly  became  worse,  and  died  in  about  ten  hours  after  the  acci- 
dent. His  assistant  was  also  taken  ill,  and  died  about  fifteen  hours 
later.  [Cheni.  Neics,  London,  March,  1863,  132.)  An  instance  is 
also  reported  by  Mr.  Spence,  in  which  the  fumes  of  the  acid  proved 
fatal  to  two  persons ;  the  first  of  whom  died  in  about  forty  hours, 
and  the  other  some  hours  afterward.  [Ibid.,  167.)  In  at  least  one 
of  these  cases  the  symptoms  were  delayed  for  some  hours.     In  still 


PHYSIOLOGICAL   EFFECTS.  121 

another  case,  a  man  spilled  some  uitvn:  acid  from  a  carboy,  and  in 
endeavorintr  to  oolleot  it  he  iniiaicd  enoii<rh  of  the  vapor  to  cause 
his  death.  {Neir  Remedies,  1880,  ;32.)  In  the  well-known  case  of 
Mr.  Haywood,  who  inhaled  the  fumes  arising  from  a  mixture  of 
nitric  and  sulphuric  acids,  the  symptoms  were  delayed  for  more  than 
tliree  hours,  and  death  occurred  in  about  eleven  hours. 

Period  when  Fatal. — Nitric  acid  has  in  several  instances  caused 
death  within  a  very  few  hours,  and  in  most  instances  in  which  death 
occurred  from  its  primary  effects,  that  event  followed  within  fortv- 
eight  hours;  but  the  patient  may  recover  from  the  primary  action  of 
the  poison  and  die  from  secondary  effects  many  months  afterward. 
Thus,  in  a  case  quoted  by  Dr.  Taylor,  death  occurred  in  one  hour  and 
three-quarters  after  the  poison  had  been  swallowed ;  while,  on  the 
other  hand,  Tartra  mentions  an  instance  in  which  death  did  not  occur 
until  after  a  period  of  eight  months  ;  and  another  is  reported  in  which 
the  patient  survived  six  months.  Out  of  fifty-six  cases  of  poisoning 
by  nitric  acid,  collected  by  Tartra,  twenty-one  of  the  patients  com- 
pletely recovered,  and  eight  partially. 

Fatal  Quantity. — In  most  of  the  instances  of  poisoning  by  this 
substance,  the  quantity  taken  was  not  ascertained.  Most  writers  on 
this  subject,  however,  agree  in  fixing  the  fatal  quantity,  for  a  healthy 
adult  under  ordinary  conditions,  at  about  tioo  drachms  of  the  concen- 
trated acid ;  yet  quantities  much  larger  than  this  have  in  several  in- 
stances been  followed  by  complete  recovery.  In  a  case  reported  by 
Dr.  J.  M.  Warren,  a  woman,  aged  thirty-four  years,  having  with 
suicidal  intent  taken  three  drachms  of  the  acid  into  her  mouth,  swal- 
lowed a  portion,  but  most  of  it  was  spit  out.  She  was  seized  with 
the  usual  symptoms,  which,  however,  after  several  days,  under  active 
treatment,  nearly  subsided ;  but  secondary  symptoms  set  in,  and  she 
died  on  the  fourteenth  day  after  the  poison  had  been  taken.  {Amer. 
Jour.  3fed.  Sei.,  July,  1850,  36.)  A  boy  two  years  old  took  into  his 
mouth  a  drachm  of  fuming  nitric  acid.  He  at  once  spat  it  out,  and 
recovered  from  its  local  effects. 

Treatment. — This  consists  in  the  speedy  administration  of 
calcined  magnesia,  chalk,  or  a  dilute  solution  of  an  alkaline  carbonate, 
followed  by  the  free  exhibition  of  oily  or  mucilaginous  drinks.  In 
every  respect,  the  treatment  is  the  same  as  that  already  mentioned  in 
sulphuric  acid  poisoning  (ante,  101). 

Post-mortem  Appearances. — These  will,  of  course,  depend 


122  NITRIC   ACID. 

somewhat  on  the  length  of  time  the  individual  survived  after  taking 
the  poison.  In  acute  cases,  the  lining  membrane  of  the  lips,  mouth, 
and  fauces  has  sometimes  a  white,  but  more  generally  a  deep  yellow 
or  even  brownish  color ;  often  large  patches  of  this  membrane  are 
entirely  removed.  The  mucous  membrane  of  the  oesophagus  is  often 
much  thickened  and  altered  in  structure,  of  a  yellow  color,  and 
readily  separated.  And  like  appearances  may  be  observed  in  the 
larynx  and  trachea,  if  the  acid  has  passed  into  these  organs.  In 
these  examinations,  as  in  sulphuric  acid  poisoning,  it  must  be  borne 
in  mind  that  the  mouth  and  oesophagus  may  exhibit  but  little  injury, 
the  stomach  being  the  part  chiefly  aifected ;  and,  on  the  other  hand, 
that  the  whole  of  the  local  injury  may  be  confined  to  the  mouth  and 
air-passages,  little  or  none  of  the  poison  having  been  swallowed.  In 
an  instance  of  poisoning  by  this  acid  quoted  by  Dr.  Christison,  it 
left  no  trace  of  its  passage  downward  until  it  had  arrived  near  the 
pylorus. 

The  stomach  is  usually  distended,  externally  changed  in  color, 
more  or  less  inflamed,  and  adherent  to  the  neighboring  organs.  The 
contents  of  this  organ  have  frequently  a  yellow  color,  due  to  the 
action  of  the  acid  upon  the  contained  matters.  The  mucous  mem- 
brane is  often  greatly  disorganized  and  much  changed  in  color,  and 
the  blood-vessels  are  injected  with  dark  coagulated  blood.  In  the 
case  reported  by  Dr.  Warren,  the  stomach  externally  was  of  a  purple 
color,  and  adherent  to  the  neighboring  parts;  internally  it  was  of  a 
greenish-yellow  color,  and  its  tissues  were  so  softened  that  it  could 
not  be  separated  from  the  surrounding  parts  without  being  greatly 
lacerated.  When  the  coats  of  the  stomach  are  perforated  by  the  acid, 
— which,  however,  rarely  happens, — the  contents  of  the  organ  may 
escape  into  the  abdomen  and  cause  a  yellow  coloration  and  great  dis- 
organization of  all  the  neighboring  viscera. 

The  small  intestines,  particularly  the  upper  portion,  may  exhibit 
appearances  similar  to  those  found  in  the  stomach ;  often,  however, 
they  entirely  escape  the  direct  action  of  the  acid,  it  not  passing  below 
the  stomach.  The  large  intestines  are  usually  filled  with  hard  fseces. 
The  other  abdominal  organs  are  often  more  or  less  highly  inflamed, 
even  when  the  stomach  is  not  perforated;  the  bladder  is  usually 
empty,  no  urine  having  been  secreted. 

In  Dr.  Stevenson's  case,  in  which  three  ounces  of  the  acid  proved 
fatal  in  seventeen  hours,  the  lips  and  angles  of  the  mouth  were  found 


GENERAL  CHEMICAL  NATURE.  123 

discolored  yellow,  and  also  a  portion  of  the  tongue.  Beyond  this 
the  mucous  surface  of  the  alimentary  canal,  as  far  as  the  stomach, 
was  white,  and  covered  with  a  thin  paint-like  coat  of  milky  opacity. 
At  the  lower  end  of  the  oesophai^us  the  mucous  membrane  was  partly 
removal.  The  pharynx  was  much  swollen,  with  its  cavity  somewhat 
narrowed.  The  larynx  exhibited  signs  of  decreasing  inflammation 
from  above  downward.  The  stomach  contained  a  small  jjerforation 
on  the  anterior  surface,  half  an  inch  from  the  lower  border.  Close 
around  the  perforation,  the  i)eritoneum  was  ecchymo.sed,  but  no  lymph 
was  exuded.  The  walls  of  the  stomach  were  collapsed  in  stiffened 
folds,  and  at  several  points  were  nearly  perforated.  The  gastric 
mucous  membrane  was  covered  with  a  deep  reddish-brown  gritty 
paste,  which  was  neutral  to  litmus.  The  duodenum  showed  slough- 
ing of  the  valvulae  conniventes.  The  jejunum  and  ileum  were 
natural,  but  their  contents  consisted  of  tarry  blood,  especially  in  the 
ileum.  The  right  side  of  the  heart  contained  a  clot  of  black  l)lood. 
When  the  patient  survives  the  primary  effects  of  the  poison  and 
dies  from  secondary  results,  the  body  is  greatly  emaciated,  and  the 
stomach  and  other  portions  of  the  alimentary  canal  are  more  or  less 
contracted,  their  walls  thickened  and  the  cavities  nearly  closed.  Stric- 
ture of  the  oesophagus  has  not  unfrequently  occurred,  and  the  pyloric 
end  of  the  stomach  has  been  so  greatly  contracted  as  nearly  to  oblit- 
erate its  opening.  In  some  few  instances,  the  stomach  was  so  far 
destroyed  that  no  part  of  its  structure  could  be  distinguished. 

Chemical  Properties. 

General  Chemical  Xature. — Anhydrous  nitric  acid,  or  nitric 
anhydride,  is  a  compound  of  the  elements  Nitrogen  and  Oxygen,  in 
the  proportion  of  two  atoms  of  the  former  to  five  of  the  latter,  XgO^. 
It  is  a  transparent,  colorless,  crystalline  solid;  in  this  state  it  melts 
at  30°  C.  (86°  F.),  and  boils  at  about  45°  C.  (113°  R):  it  was  first 
obtained,  in  1849,  by  Deville.  In  combination  with  water,  it  has 
long  been  known  under  the  name  of  aquafortis,  which,  in  its  most 
concentrated  form,  consists  of  one  molecule  of  nitric  anhydride  in 
combination  with  one  molecule  of  water,  the  combination  forming 
two  molecules  of  nitric  acid,  HXO3;  thus:  1100  +  ^205=  2HXO3. 

In  its  pure  state,  nitric  acid  is  a  colorless,  intensely  corrosive  acid 
liquid,  which,  in  its  most  concentrated  form,  has  a  density  of  about 
1 .520,  and  contains  85.72  per  cent,  of  the  anhydrous  acid.    The  density 


124 


NITRIC    ACID. 


of  the  acid  of  the  shops  usually  varies  from  1.350  to  1.450.  Con- 
centrated nitric  acid  is  one  of  the  most  powerfully  corrosive  substances 
known.  It  imparts  a  yellow  stain  to  the  skin,  nails,  wool,  and  other 
organic  substances.  Exposed  to  the  air,  it  emits  white  fumes  ;  when 
mixed  with  water,  it  evolves  a  sensible  amount  of  heat.  It  boils  at 
about  84.5°  C.  (184°  F.),  and  freezes  at  —40°  C.  (—40°  F.).  When 
the  concentrated  acid  is  boiled,  it  diminishes  in  density  and  its  boiling 
point  increases,  until  the  liquid  acquires  a  density  of  about  1.424, 
when  it  distils  chiefly  in  the  form  of  a  hydrate  of  the  acid,  con- 
sisting of  three  molecules  of  water  with  two  of  the  acid  (SHaO ; 
2HNO3). 

The  following  table,  according  to  Dr.  Ure,  indicates  approxi- 
matively  the  percentage  by  weight  of  nitric  anhydride,  NgO^,  in  pure 
aqueous  solutions  of  different  specific  gravities : 

STRENGTH    OF    AQUEOUS    SOLUTIONS    OF    NITRIC    ACID. 


Percent- 

Percent- 

Percent- 

Percent- 

Sp. Ge. 

age  OF 

Sp.  6e. 

age  OF 

Sp.  Ge. 

age  OF 

Sp.  Gr. 

age  OF 

N2O6. 

N2O6. 

N2O5. 

N2O5. 

1.500 

79.7 

1.402 

56.6 

1.258 

35.1 

1.117 

16.7 

1.491 

76.5 

1.383 

53.4 

1.246 

33.5 

1.093 

13.5 

1.479 

73.3 

1.363 

50.2 

1.221 

30.3 

1.071 

10.4 

1.467 

70.1 

1.343 

47.0 

1.196 

27.1 

1.048 

7.2 

1.453 

66.9 

1.322 

43.8 

1.183 

25.5 

1.027 

4.0 

1.439 

63.8 

1.300 

40.4 

1.171 

23.9 

1.016 

2.4 

1.419 

59.8 

1.283 

38.3 

1.146 

20.7 

1.005 

0.8 

Nitric  acid  as  found  in  commerce  is  frequently  more  or  less 
colored,  the  color  being  due  to  the  presence  of  some  of  the  lower 
oxides  of  nitrogen,  and  varying  from  a  light  yellow  to  an  orange- 
red.  In  this  state  it  is  even  more  corrosive  than  the  pure  acid.  It 
is  not  unfrequently  contaminated  with  sulphuric  and  hydrochloric 
acids  and  other  impurities. 

The  salts  of  nitric  acid  are  for  the  most  part  colorless,  and  very 
freely  soluble  in  water.  They  are  all  decomposed  by  a  red  heat. 
Their  aqueous  solutions  are  also  decomposed  when  heated  with  free 
sulphuric  acid,  with  the  formation  of  a  sulphate,  the  nitric  acid 
being  eliminated  in  its  free  state. 

Special  Chemical  Properties. — Nitric  acid  very  readily 
parts  with  a  portion  of  its  oxygen.  When  brought  in  contact  with 
many  of  the  metals,  such  as  copper,  zinc,  iron,  or  tin,  it  is  in  part 


SPECIAL   CHEMICAL    PROPERTIES.  125 

decomposed  with  great  rapidity,  with  the  formation  of  a  nitrate  and 
the  evolution  of  one  or  more  of  the  lower  oxides  of  nitrogen  in  the 
form  of  deep  red  fumes.  The  evolution  of  these  fumes  is  quite 
characteristic  of  the  acid. 

When  a  nitrate,  in  its  dry  state,  is  brought  in  contact  with 
ignited  charcoal,  the  latter  l)urns  vividly  at  the  expense  of  the 
oxygen  ol'  the  nitric  acid,  the  salt,  if  an  alkaline  compound,  being 
converted  into  a  carbonate. 

On  account  of  the  free  solubility  of  the  compounds  of  nitric 
acid,  it  cannot  be  precipitated  from  solution  by  reagents ;  however, 
the  presence  of  very  minute  traces  of  the  acid  can  be  detected  with 
great  certainty.  When  not  too  much  diluted,  it  may  be  recognized 
by  the  properties  already  mentioned.  In  the  following  examination 
of  the  behavior  of  solutions  of  nitric  acid,  the  fractions  employed 
express  the  fractional  part  of  a  grain  of  nitric  anhydride  present  in 
one  grain  of  the  solution. 

1.    Copper  Test. 

When  tolerably  strong  nitric  acid  is  treated  in  a  test-tube  with 
a  slip  of  copper-foil,  the  acid  is  decomposed  with  the  formation  of 
copper  nitrate,  water,  and  the  evolution  of  nitrogen  dioxide,  which 
latter  on  coming  in  contact  with  the  air  is  oxidized^  and  escapes  in 
the  form  of  deep  red  fumes  of  nitrogen  tetroxide ;  the  copper  nitrate 
thus  formed  imparts  to  the  liquid  a  more  or  less  greenish  color. 
These  reactions  are  expressed  by  the  following  formulse:  8HXO3  + 
Cu3= 3Cu  2NO3  +  4H2O  +  N26, ;  and  XA  +  02=  ^Pr 

When  the  acid  is  more  dilute,  it  is  not  acted  upon  by  copper 
unless  the  mixture  be  heated  or  free  sulphuric  acid  be  added,  and 
the  gas  evolved  may  be  colorless ;  its  presence,  however,  may  be 
recognized  by  its  peculiar  odor,  acid  reaction,  and  by  rendering  blue 
a  piece  of  starch-paper  moistened  with  a  solution  of  iodide  of  potas- 
sium. In  the  presence  of  sulphuric  acid,  the  whole  of  the  nitric 
acid,  whether  in  its  free  state  or  as  a  nitrate,  is  evolved  finally  in 
the  form  of  nitrog-en  tetroxide. 

The  following  results  refer  to  the  behavior  of  Jive  fluid-grains  of 
the  nitric  acid  solution  with  a  very  small  slip  of  copper-foil. 
1.   1-lOth  solution,  or  half  a  grain  of  anhydrous  nitric  acid,  fails  to 
be  acted  upon  by  the  copper  till  heat  is  applied, — then  decom- 
position takes  place  quite  briskly,  yielding  quite  perceptible  red 


126  NITRIC   ACID. 

vapors,  which  quickly  redden  moistened  litmus-paper,  and 
impart  a  blue  color  to  starch-paper  prepared  as  above.  The 
liquid  assumes  a  very  marked  greenish-blue  color. 

2.  1— 20th  solution  yields  only  a  feeble  reaction,  even  on  the  appli- 

cation of  heat;  but  if  a  few  drops  of  concentrated  sulphuric 
acid  be  added,  there  is  a  brisk  reaction,  and  ultimately  the 
liquid  acquires  a  very  distinct  greenish-blue  color. 

3.  1— 50th  solution  gives  no  evidence  of  decomposition  by  heat  alone ; 

but  with  sulphuric  acid  and  heat  it  yields  a  brisk  reaction  and 
a  light  greenish-blue  solution.  If  this  experiment  be  performed 
in  a  very  narrow  tube,  the  evolved  gas  imparts  a  distinct  red- 
dish hue  to  the  contained  air. 

4.  1-1 00th  solution,  under  the  influence  of  a  few  drops  of  sulphuric 

acid  and  heat,  yields  a  quite  good  effervescence  around  the 
surface  of  the  copper,  and  the  liquid  acquires  a  faint  greenish- 
blue  color. 

5.  l-500th  solution,  under  the  same  influences  as  4,  yields  a  very 

distinct  effervescence,  and  after  a  time  the  fluid  acquires  a 
perceptible  greenish  tint. 

6.  1-1 000th  solution  yields  a  perceptible  reaction. 

Results  similar  to  the  above  may  be  obtained  from  the  acid 
when  in  the  form  of  a  nitrate;  but  then  the  addition  of  sulphuric 
acid  is  necessary  in  all  cases.  If  the  nitrate  to  be  tested  is  in  the 
solid  state,  it  should  be  dissolved  in  the  least  practicable  quantity 
of  water ;  on  the  other  hand,  if  it  is  in  solution,  the  liquid  should 
be  concentrated  as  far  as  practicable  before  the  test  is  applied.  In 
the  use  of  this  test,  it  must  be  kept  in  mind  that  sulphuric  acid 
not  unfrequently  contains  traces  of  nitric  acid  :  the  presence  of  this 
impurity  could,  of  course,  be  determined  by  the  test  itself  before  it 
is  applied  to  a  suspected  solution. 

2.   Gold  Test. 

If  a  solution  of  free  nitric  acid  or  of  a  nitrate  be  heated  with 
excess  of  pure  hydrochloric  acid,  the  two  acids  react  upon  each  other 
and  eliminate  free  chlorine,  which  has  the  property  of  dissolving 
gold-leaf  to  the  form  of  chloride  of  gold.  The  presence  of  the 
gold  compound  can  be  recognized,  when  present  in  not  too  minute 
quantity,  by  a  solution  of  chloride  of  tin,  which  produces  a  purple 
precipitate,  or  at  least  imparts  a  purplish  color  to  the  liquid. 


IRON    TEST.  127 

Before  applying  this  test  to  a  suspected  solutioi),  the  liydrocliloric 
acid  about  to  he  employed  should  be  tested  alone,  in  order  to  deter- 
mine whether  it  is  entirely  free  from  uncoinbined  chlorine,  which  is 
often  present. 

When  one  grain  of  the  nitric  acid  solution  is  mixed,  in  a  small 
test-tube,  with  five  fluid-grains  of  tolerably  strong  hydrochloric  acid 
and  a  vei-y  small  slip  of  gold-leaf,  the  mixture  on  being  heated  to 
the  boiling  temperature  yields  the  following  results: 

1.  y-J-y-  grain  of  nitric  anhydride:  in  a  very  little  time  the  gold  dis- 

solves ;  the  cooled  solution  yields  with  the  tin  reagent  no  imme- 
diate change,  but  after  a  little  time  it  assumes  a  decided  purple 
color. 

2.  Y»oT  gi'S'ii  '•  after  a  little  time  the  gold  dissolves,  and  the  cooled 

solution  yields  with  the  tin  compound  a  faint  purple  color. 

3.  -5-oVu"  grain,  after  several  minutes,  dissolves  a  very  minute  quan- 

tity of  gold;  but  the  solution  fails  to  yield  satisfactory  results 

with  the  tin  reagent. 
These  reactions  are  also  common  to  solutions  of  chlorates,  hypo- 
chlorites, chromates,  iodates,  and  bromates.  The  same  is  also  true 
of  the  per-combinations  of  iron,  as  first  pointed  out  by  Henry 
Wurtz.  [Chem.  Gaz.,  xvii.  32.)  This  metal  is  readily  separated  by 
treating  the  solution  with  sodium  carbonate  and  filtration.  It  need 
hardly  be  added  that  a  nitrate  may  be  distinguished  from  all  of 
these  fallacious  salts  by  the  action  of  the  preceding  test. 

3,  Iron  Test. 

When  free  nitric  acid,  or  a  solution  of  a  nitrate,  is  mixed  with 
several  times  its  volume  of  concentrated  sulphuric  acid  and  the  cooled 
mixture  treated  with  a  crystal  of  sulphate  of  iron  {ferrous  sulphate), 
the  latter  after  a  time  becomes  surrounded  by  a  blackish-brown, 
brownish,  or  purple  compound,  which  is  said  to  consist  of  2FeS04; 
NO,  the  reaction  in  the  case  of  free  nitric  acid  being:  2HXO3-I- 
SH^SO.-f  10FeSO,  =  3re23SO,-f4Hp-|-2  (2FeS0,;  NO). 

Instead  of  using  the  iron  salt  in  its  solid  state,  it  is  more  satis- 
factory to  employ  it  in  the  form  of  a  saturated  solution.  To  thus 
apply  the  test,  a  drop  of  the  nitric  acid  solution  is  thoroughly  mixed 
in  a  small  test-tube  with  eight  or  ten  times  its  volume  of  sulphuric 
acid,  the  mixture  gently  M'armed  for  a  little  time,  then  cooled  by 
immersing  the  tube  in  cold  water;  a  drop  of  the  iron  solution  is 


128  NITRIC    ACID. 

then  allowed  to  flow  down  the  inside  of  the  tube  upon  the  acid 
mixture,  when  the  stratum  where  the  two  liquids  are  in  contact  will 
acquire  a  beautiful  purjjle  or  brownish-purple  color,  the  tint  depend- 
ing on  the  quantity  of  nitric  acid  present ;  on  now  slowly  mixing 
the  liquids  by  means  of  a  glass  rod,  taking  great  care  that  no  heat 
is  evolved,  the  same  coloration  will  be  observed  throughout  the 
mixture. 

1.  -j-i-g-  grain  of  nitric  anhydride,  in  one  fluid-grain  of  water,  when 

treated  as  above,  the  contact  surfaces  of  the  iron  and  acid  liquids 
present  a  beautiful  purple  line;  on  carefully  mixing  the  liquids, 
the  mixture  assumes  a  deep  purple  color,  and  soon  begins  to 
effervesce,  gives  out  the  odor  of  nitrogen  tetroxide,  and  the  color 
becomes  discharged.  On  the  addition  of  another  drop  of  the 
iron  solution,  the  color  is  reproduced. 

2.  YFTo   S^^^^  yields  a  beautiful  purple  mixture,  which  remains 

unchanged  for  at  least  several  hours. 

3.  s-qVo   gi'sin  •  on   mixing  the  two  solutions,  they  assume  a  very 

decided  purplish  tint,  which  is  permanent  for  some  hours. 

4.  Yo'.Wo  gi'aiii :  the  mixed  liquids  assume  a  distinct  purplish  hue, 

which  after  some  hours  becomes  pinkish.  These  colors  are  best 
seen  by  inclining  the  tube  over  a  piece  of  white  paper. 
Much  the  same  results  as  those  just  described  may  be  obtained 
by  employing  the  iron  compound  in  the  solid  state;  its  solution, 
however,  is  preferable.  In  all  cases,  before  applying  this  test  to  a 
suspected  solution,  the  sulphuric  acid  should  be  tested  alone :  in  fact, 
it  is  somewhat  difficult  to  find  that  acid  in  the  shops  entirely  free 
from  traces  of  nitric  acid  or  some  of  the  lower  oxides  of  nitrogen. 

4.  Indigo  Test. 

When  a  solution  of  nitric  acid,  or  of  a  nitrate,  is  mixed  with 
hydrochloric  acid  or  chloride  of  sodium,  as  recommended  by  Liebig, 
and  the  mixture  colored  by  a  solution  of  indigo,  then  heated  with 
sulphuric  acid,  the  chlorine  set  free  through  the  agency  of  the  nitric 
acid  will  discharge  the  blue  color  of  the  mixture.  In  applying  this 
test,  a  small  quantity  of  the  nitric  acid  solution  is  treated  with  a  few 
crystals  of  pure  common  salt  or  a  drop  of  hydrochloric  acid  and  just 
enough  of  a  strong  sulphuric  acid  solution  of  indigo  to  impart  a  dis- 
tinct blue  tint ;  the  mixture  is  then  heated,  and  while  hot  a  few  drops 
of  concentrated  sulphuric  acid  cautiously  added  and  mixed  with  the 


BRUOINE   TEST.  129 

liquid,  after  which,  if  necessary,  the  heat  is  continued  until  the  blue 

tint  of  tho  fluid  disappears. 

The  following'  results  refer  to  tiie  behavior  of  five  grainn  of  the 

nitric  acid  solution. 

1.  1-1 00th  solution,  when  treated  as  above,  the  blue  color,  on  the 
addition  of  a  few  drops  of  sulphuric  acid  to  the  heated  mixture, 
is  immediately  discharged,  and  the  liquid  assumes  a  yellow  color. 

jJ.   1-1 000th  solution  yields  much  the  same  results  as  1. 

3.  l-10,000th  solution:  the  blue  color  is  not  discharged  until  the 

mixture  is  heated  some  minutes  with  several  drops  of  sulphuric 
acid  ;  the  liquid  then  acquires  a  faint  yellow  tint. 

4.  1 -20,000th  solution  behaves  much  the  same  as  3. 

5.  l-50,000th  solution  requires  to  be  boiled  several  minutes  with 

several  drops  of  sulphuric  acid  before  the  blue  tint  disappears. 
For  the  success  of  this  reaction  it  is  necessary  to  employ  the 
merest  trace  of  indigo,  the  tint  of  which  is  best  seen  by  inclining 
the  tube  containing  the  mixture  over  white  paper. 
It  is  well  known  that  chlorates,  chromates,  iodates,  binoxide  of 
manganese,  and  several  other  similar  compounds  have,  like  nitric 
acid,  the  property  of  evolving  chlorine  from  hydrochloric  acid,  and 
therefore  of  bleaching  a  solution  of  indigo ;  and  Wurtz,  in  his  valu- 
able paper  already  referred  to,  has  shown  that  the  chlorides  of  gold, 
platinum,  and  tin  bleach  an  indigo  solution,  even  without  the  presence 
of  hydrochloric  acid,  and  that  in  the  presence  of  this  acid,  arsenic 
acid  has  a  similar  property.     It  is  not  likely,  however,  that  either  of 
these  fallacious  substances  would  be  present  in  a  medico-legal  investi- 
gation for  nitric  acid. 

Much  more  probable  sources  of  error  than  either  of  those  just 
mentioned,  to  be  guarded  against,  are  the  presence  of  free  chlorine 
in  the  hydrochloric  acid,  and  that  of  traces  of  nitric  acid  or  some  of 
the  lower  oxides  of  nitrogen  in  the  sulphuric  acid  employed.  No  reli- 
ance whatever  could  be  placed  in  this  test  when  applied  to  organic 
mixtures. 

5.  Brucine  Test. 

This  test,  which  was  first  suggested  by  Berthemont,  is  based  on 
the  production  of  a  blood-red  color  when  nitric  acid  or  a  nitrate  is 
mixed  with  a  sulphuric  acid  solution  of  brucine.  Pure  brucine, 
when  added  to  pure  sulphuric  acid,  assumes  a  pale  pink  color  and 

9 


130  NITRIC   ACID. 

slowly  dissolves  to  a  colorless  or  nearly  colorless  solution,  unless  the 
proportion  of  alkaloid  be  comparatively  large,  when  the  solution  has 
a  pinkish  hue. 

When  one  grain  of  the  free  nitric  acid  solution  or  of  a  nitrate  is 
mixed,  for  convenience  in  a  white  porcelain  dish,  with  about  five 
fluid-grains  of  concentrated  sulphuric  acid,  and  a  few  crystals  of 
brucine  added,  if  the  solution  contains  : 

1.  yl-g-  grain   of  anhydrous   nitric  acid,   the  brucine    immediately 

assumes  a  red-orange  color,  and,  on  being  stirred,  dissolves  to  a 
solution  of  the  same  hue,  which  very  slowly  fades  to  bright 
yellow. 

2.  YoWo  gi^ain :  the  alkaloid  acquires  a  red  color,  and  yields  a  dull 

orange  solution,  which  slowly  becomes  yellow. 

3.  g-oVo"  grain  :  the  brucine  assumes  a  rose-pink  color,  and  dissolves 

to  a  solution  having  a  decided  reddish-pink  hue,  which  changes 
to  faint  orange,  then  fades  to  yellow. 

4.  Yo".Wo  grain  :  the  crystals  acquire  a  pink  color,  and  dissolve  to  a 

solution  of  the  same  tint,  which  becoming  amber  changes  to 
yellow. 

5.  -25-,Vfo   gi'ain  :   the  brucine  assumes  a  reddish  color,  and,  when 

stirred  in  the  mixture,  imparts  to  it  a  decided  amber  color,  which 
soon  changes  to  light  yellow. 

Q-g-  grain  :  the  alkaloid  becomes  slightly  colored,  and  yields  a 
solution  of  a  faint  amber  hue,  which  quickly  changes  to  very 
light  yellow.     These  colors  are  quite  feeble,  yet  when  the  re- 
action is  compared  with  that  obtained  from  the  alkaloid  and 
sulphuric  acid  alone,  the  difference  is  very  well  marked. 
When  the  nitric  acid  is  in  the  solid  state  in  the  form  of  a  nitrate, 
the  reaction  of  this  test  is  even  more  delicate  than  when  applied  to 
solutions.     Under  these  circumstances,  a  very  small  portion  of  the 
salt,  or  the  residue  left  on  evaporating  its  solution  to  dryness,  is  dis- 
solved in  a  few  drops  of  sulphuric  acid,  and  then  a  crystal  or  two  of 
the  alkaloid  added.     The  residue  obtained  from  a  solution  of  potas- 
sium nitrate  containing  only  the  l-100,000th  of  a  grain  of  nitric 
acid,  when  moistened  with  a  very  small  drop  of  sulphuric  acid  con- 
taining a  little  brucine,  immediately  assumes  a  distinct  orange  color, 
and  dissolves  to  a  brick-dust  pink  solution,  the  tint  of  which  soon 
fades  to  faint  yellow. 

This  test  furnishes  the  most  ready  and  delicate  means  of  deter- 


i_ 

50,0 


NARCOTINE   TEST.  131 

niiiiiiiLi-  tlif   i)iirity  of  sulplmric  acid    in   regard   to  the  presence  of 
traces  of  nitric  acid. 

A  sulplinric  acid  solution  of  briicino  also  pnxluces  a  soinewliat 
similar  coloration  with  chloric  acid  and  its  salts.  But  the  most 
minute  quantity  of  a  salt  of  this  kind  imparts  a  strong  yellow,  and 
a  very  small  quantity  an  orange  color,  to  sulphuric  acid  alone,  and 
evolves  fumes  of  chlorine  tetroxide,  having  a  greenish  color  and 
peculiar  odor.  To  guard  against  this  fallacy,  therefore,  it  is  only 
necessary  to  observe  the  action  of  the  sulphuric  acid  alone.  But, 
besides  this  fallacy,  there  are  certain  other  oxidizing  agents  that  will 
produce  with  sulphuric  acid  and  brucine  a  coloration  similar  to  that 
caused  by  nitric  acid. 

6.  Narcotine  Test. 

AVhen  a  small  quantity  of  narcotine  is  added  to  a  few  drops  of 
pure  concentrated  sulphuric  acid,  the  alkaloid  dissolves  to  a  light- 
yellow  solution,  which  when  heated  assumes  a  purplish  color;  but  if 
free  nitric  acid  or  a  nitrate  be  present,  the  narcotine  dissolves  to  a 
reddish-brown  solution,  which  on  the  application  of  a  gentle  heat 
acquires  a  deep  blood-red  color.  Mialhe  was  the  first  to  employ  this 
reaction  as  a  test  for  nitric  acid. 

When  one  grain  of  the  nitric  acid  solution  is  mixed  with  five 
fluid-grains  of  sulphuric  acid,  and  the  mixture  allowed  to  cool,  the 
addition  of  a  few  crystals  of  narcotine  produces  the  following  results  : 

1.  Y^  grain  of  nitric  anhydride  :  the  alkaloid  assumes  a  deep  brown 

color,  and  imparts  to  the  liquid  a  decided    brownish-yellow 
color,  which  by  heat  is  changed  to  a  permanent  deep  blood-red. 

2.  YoVd  grain :  the  narcotine  dissolves  to  a  decided  reddish  solution, 

which  when  heated  assumes  a  fine  blood-red  color. 

^'  TuVo  grain  yields  a  distinct  reddish  color,  which  is  changed  to 
reddish-brown  by  heat. 

4.  To.Wo  grain :  the  solution  of  the  alkaloid  has  a  faint  reddish 
tint,  which  by  heat  is  changed  to  a  purple-red.  This  last 
color  might  be  readily  confounded  with  that  from  narcotine 
alone;  but  this  alkaloid  singly  would  not  impart  the  primary 
reddish  tint. 
When  the  nitric  acid  is  in  solution  in  the  form  of  a  nitrate,  the 

liquid  should  be  evaporated,  and  the  dry  residue  dissolved  in  a  few 

drops  of  colorless  sulphuric  acid,  then  tested  by  a  few  crystals  of 


r 


132  NITEIC   ACID. 

narcotine.     Under  these  conditions,  given  quantities  of  the  acid  yield 
even  stronger  colors  than  described  above. 

7.  Aniline  Test. 

This  test,  first  advised  by  M.  Braun  {Jour,  de  Chim.,  1867,  637), 
takes  advantage  of  the  production  of  a  red  color,  due  to  the  for- 
mation of  fuchsine,  when  a  drop  of  diluted  nitric  acid  or  of  a  nitrate 
is  added  to  a  mixture  of  a  sulphuric  acid  solution  of  aniline  and 
concentrated  sulphuric  acid. 

The  aniline  solution  may  be  prepared  by  dissolving  one  part  of 
pure  aniline,  or  its  equivalent  in  the  form  of  sulphate,  in  one  hun- 
dred parts  of  a  mixture  of  four  parts  of  water  and  one  part  of  con- 
centrated sulphuric  acid.  A  few  drops  of  this  solution  are  now  added 
to  about  ten  drops  of  pure  concentrated  sulphuric  acid  contained  in 
a  watch-glass  or  small  porcelain  dish,  after  which  a  drop  of  the  nitric 
acid  solution  or  a  small  fragment  of  solid  nitrate  is  added  to  the 
mixture.  Sooner  or  later  fringes  of  a  more  or  less  intense  red  color 
make  their  appearance,  and  after  a  time  the  whole  mixture  acquires 
a  more  or  less  deep  red  color. 

To  obtain  the  best  results  by  this  test,  it  is  necessary  that  the  pro- 
portions of  nitric  acid  and  aniline  present  be  within  certain  limits. 
In  the  presence  of  large  excess  of  the  acid,  the  color  fails  to  appear, 
or  is  quickly  discharged;  whilst,  on  the  other  hand,  in  the  presence 
of  large  excess  of  the  aniline  solution,  the  coloration  is  diminished 
in  intensity.  With  a  drop  of  a  solution  containing  1-lOOth  of  its 
weight  or  more  of  nitric  acid,  three  or  four  drops  of  the  aniline  solu- 
tion should  be  employed.  Under  proper  conditions,  the  red  colora- 
tion remains  unchanged  for  many  hours.  The  production  of  the  red 
color  is  much  facilitated,  and  the  delicacy  of  the  reaction  increased, 
by  gently  warming  the  mixture. 

1.  Y^  grain  of  nitric  anhydride  soon  produces,  under  the  test,  red  or 

rose-red  fringes,  and  after  a  time  the  mixture  acquires  a  beauti- 
ful red  coloration. 
If,  after  the  addition  of  the  nitric  acid,  the  mixture  be  warmed, 

immediately  deep  red  fringes  appear,  and  quickly  the  whole  assumes 

a  beautiful  deep  orange-red  color. 

2.  YooT  grain  :  on  warming  the  mixture,  quickly  produces  a  rose-red 

coloration.     Without  the  application  of  heat  little  or  no  color 
appears. 


IODINE   AND   OTHER   TESTS.  133 

3.  ^TsViF  gi^'"  '•    on    warming   the    mixture,  it   quickly   assumes   a 

very  distinct  pinkish  hue,  wliich  remains  unchanged  for  some 
hours. 

4.  jTj-.'oTTir  gi'^'"  o'  nitric  aniiydride  fails  to  impart  to  the  warmed 

mixture  any  very  distinct  coloration. 

The  above  results  apply  equally  to  nitric  acid  in  its  free  state 
and  when  in  the  form  of  a  nitrate.  Under  the  action  of  the  test, 
similar  colorations  are  developed  by  hyponitrous  and  nitrous  acids, 
and  nitrites. 

Chloric  and  chromic  acids  and  their  salts  impart  to  the  reagent 
mixture  a  deep  blue  color.  In  the  case  of  chloric  acid,  the  blue  colora- 
tion appears  even  in  the  presence  of  1-lOOOth  grain  of  the  acid  ;  but 
with  more  minute  quantities,  even  up  to  l-10,000th  grain,  the  mix- 
ture acquires  a  reddish  or  purple  hue,  which  might  be  confounded 
with  the  reaction  of  minute  quantities  of  nitric  acid.  But  on  gently 
warming  the  mixture,  the  reddish  color  produced  by  traces  of  chloric 
acid  is  quickly  changed  to  blue;  whereas  the  red  color  caused  by 
nitric  acid  is  much  increased  in  intensity. 

loDiXE  Test. — This  method,  first  proposed  by  J.  Higgin  [Chem. 
Gaz.,  viii.  249),  takes  advantage  of  the  property  possessed  by  nitric 
acid  of  decomposing  hydriodic  acid  with  the  evolution  of  free  iodine, 
and  the  ready  detection  of  the  latter  by  means  of  starch.  To  apply 
this  test,  the  suspected  solution  is  mixed  with  about  one-sixth  of  its 
volume  of  concentrated  sulphuric  acid  and  heated  to  near  the  boiling 
temperature  for  several  minutes,  then  allowed  to  cool ;  the  mixture 
is  then  treated  with  a  drop  of  starch  mucilage  and  a  few  drops  of  a 
very  dilute  solution  of  iodide  of  potassium,  when,  if  nitric  acid  is 
present,  the  liquid  acquires  a  more  or  less  blue  color.  The  author 
of  this  method  states  that  a  l-20,000th  solution  of  the  acid  yields  in 
a  few  minutes  a  decided  blue  coloration.  It  must  be  remembered, 
however,  that  sulphuric  acid  alone  will,  after  a  time,  liberate  iodine, 
ev^en  from  very  dilute  solutions  of  iodide  of  potassium. 

Other  Tests. — Mr.  J.  C.  Schaeffer  has  suggested  a  test,  which 
depends  on  the  conversion  of  nitric  acid  into  nitrous  acid  by  the 
action  of  metallic  lead,  and  the  production  of  a  rich  yellow  color 
when  the  liquid  is  treated  with  potassium  ferrocyanide  and  acetic 
acid.  [Chem.  Gaz.,  ix.  289.)  In  somewhat  strong  solutions  of  the 
acid  this  reaction  is  well  marked  ;  but,  as  the  reagent  alone  yields  a 


134  NITRIC   ACID. 

yellow  coloration,  it  is  not  applicable  for  the  detection  of  the  acid 
when  much  diluted. 

Mr.  J.  Horsley  has  proposed  a  test,  which  is  applied  as  follows : 
A  small  quantity  of  water,  acidulated  with  a  few  drops  of  sulphuric 
acid,  is  placed  in  a  small  test-tube,  and  a  small  portion  of  pyrogallic 
acid  added,  after  which  a  little  concentrated  sulphuric  acid  is  allowed 
to  flow  down  the  inside  of  the  tube  and  subside  to  the  bottom  of 
the  mixture;  a  few  crystals  of  chloride  of  sodium  are  then  added, 
and,  after  the  effervescence  has  ceased,  a  small  quantity  of  the  solid 
nitrate  to  be  examined  is  dropped  into  the  mixture,  when  the  subsided 
acid,  in  a  very  little  time,  assumes  an  intense  purple  or  deep  orange- 
brown  color,  which  may  ultimately  extend  throughout  the  entire 
mixture.  [London  Chem.  News,  June,  1863,  268.)  We  can  con- 
firm the  statement  of  Mr.  Horsley  in  regard  to  the  extreme  delicacy 
of  this  reaction,  the  smallest  particle  of  a  nitrate  yielding  a  very 
satisfactory  coloration. 

Separation  from  Organic  Mixtures. 

Suspected  Solutions. — If  the  suspected  liquid  has  a  strong  acid 
reaction  and  is  free  from  suspended  solid  matters,  even  though  it  is 
somewhat  colored,  a  portion  of  it  may  be  examined  at  once,  by  being 
placed  in  a  small  test-tube  with  a  slip  of  copper,  when  if  the  fluid 
contains  one-third  or  more  of  its  volume  of  the  ordinary  nitric  acid 
of  the  shops,  it  will  immediately  be  acted  upon  by  the  metal,  give  oflP 
red  fumes  and  yield  a  greenish-blue  solution.  If  this  reaction  fail, 
the  mixture,  after  the  addition  of  sulphuric  acid  if  necessary,  is 
gradually  heated,  and  any  evolved  gas  examined  in  regard  to  its 
color,  odor,  and  with  wet  litmus-paper  and  starch-paper  moistened 
with  a  solution  of  iodide  of  potassium,  in  the  manner  already  directed. 
A  very  good  method  of  applying  this  test,  when  the  quantity  of 
liquid  is  limited,  is  to  warm  a  few  drops  of  the  suspected  solution 
with  several  drops  of  sulphuric  acid  and  a  slip  of  copper  in  a  watch- 
glass  covered  by  an  inverted  glass  containing  separate  slips  of  the 
moistened  litmus-  and  starch-papers.  In  applying  this  method,  it 
must  be  remembered  that  when  a  sulphuric  acid  solution  of  a  chloride 
is  heated  it  will  evolve  hydrochloric  acid  gas,  which  also  reddens 
litmus-paper;  and  if  any  oxidizing  substance  is  present,  a  portion  of 
the  evolved  acid  may  undergo  decomposition  with  the  elimination  of 
free  chlorine,  which  will  blue  moistened  iodized  starch-paper.     If 


SEPARATION  FROM  ORGANIC  MIXTURES.         135 

tliere  be  any  uncertainty  in  regard  to  the  true  nature  of  these  results, 
a  ])ortiou  of  the  original  solution  is  treated  with  a  saturated  solution 
of  acetate  of  silver,  when,  if  a  chloride  is  present,  it  will  yield  a  wlnte 
})recipitate  of  chloride  of  silver.  If  a  precipitate  be  thus  obtained, 
the  solution  is  treated  with  slight  excess  of  the  silver  reagent,  fil- 
tered, and  then  examined  by  the  copper  test.  Should  the  liquid 
under  examination  be  free,  or  nearly  so,  from  organic  matter,  some 
of  the  other  tests  for  the  acid  may  be  applied. 

When  these  examinations  show  the  presence  of  nitric  acid,  it  may 
become  necessary  to  prove  that  it  was  not  in  the  form  of  a  nitrate 
and  the  acidity  of  the  solution  due  to  the  presence  of  some  other 
acid.  For  this  purpose  a  portion  of  the  solution  is  evaporated  to 
dryness,  when  if  it  leave  no  saline  residue  it  follows  that  the  acid 
existed  in  its  free  state.  If,  however,  it  leave  a  saline  residue,  the 
examination  must  be  conducted  on  the  same  principles  as  pointed 
out  for  the  determination  of  sulphuric  acid  under  like  circumstances 
{ante,  115). 

Should  the  suspected  solution  be  mixed  with  solid  organic  matters, 
the  mixture,  after  the  addition  of  pure  water  if  necessary,  is  gently 
boiled  for  about  twenty  minutes,  allowed  to  cool,  filtered,  the  solids 
on  the  filter  washed,  and  the  concentrated  filtrate  tested.  In  thus 
preparing  an  organic  mixture  containing  free  nitric  acid,  it  is  well  to 
bear  in  mind  that  a  portion  of  the  acid  may  undergo  decomposition  : 
for  this  reason  it  is  sometimes  best  to  neutralize  the  acid  by  an  alkali 
before  subjecting  the  mixture  to  the  action  of  heat.  When  the  pre- 
pared liquid  contains  even  only  a  limited  quantity  of  organic  matter, 
the  copper  test  is  the  only  one  that  can  be  reliably  applied. 

Nitric  acid  may  be  separated  and  purified  from  organic  matters 
by  neutralizing  the  solution,  if  this  has  not  already  been  done,  with 
pure  carbonate  of  potassium  or  of  sodium,  whereby  the  acid  will  be 
converted  into  potassium  or  sodium  nitrate,  as  the  case  may  be;  the 
liquid  is  then,  after  filtration  if  necessary,  concentrated  at  a  moderate 
heat  until  a  small  portion  removed  to  a  watch-glass  deposits  crystals 
on  cooling,  when  the  mass  of  liquid  is  allowed  to  stand  in  a  cool 
place  until  the  crystals  have  separated.  If  the  crystals  consist  of 
potassium  nitrate,  they  will  usually  be  in  the  form  of  long  striated 
six-sided  prisms;  if  of  the  nitrate  of  sodium,  they  usually  appear  in 
the  form  of  small  obtuse  rhombohedra.  As  both  of  these  salts  are 
freely  soluble  in  water,  much  of  the  salt  may  fail  to  separate  from 


136  ISriTEIC  ACID. 

the  liquid.  The  crystals  are  now  removed  from  the  liquid,  drained 
and  dried.  By  again  concentrating  th*e  decanted  liquid,  a  second 
crop  of  crystals  may  be  obtained.  If  the  crystals  be  highly  colored, 
as  will  usually  be  the  case  when  obtained  from  very  complex  organic 
mixtures,  they  are  coarsely  powdered  and  washed  with  absolute  alco- 
hol, which  will  remove  much  of  the  foreign  matter  without  dissolv- 
ing more  than  a  mere  trace  of  the  salt.  They  are  then  dissolved, 
by  the  aid  of  a  gentle  heat,  in  a  small  quantity  of  pure  water,  and 
again  separated  by  recrystallization,  when  they  will  generally  be  suffi- 
ciently pure  for  the  application  of  any  of  the  tests.  A  small  crystal 
may  now  be  examined  by  the  bruciue  test,  and  the  result  confirmed 
by  some  of  the  other  tests,  especially  the  copper  method.  Although 
the  copper  reaction  is  the  least  delicate  of  the  several  tests  for  nitric 
acid,  yet  for  medico-legal  purposes  its  results  are  the  most  satisfactory. 

Contents  of  the  Stomach. — These  are  carefully  collected,  their 
reaction  noted,  and  then  gently  boiled  for  some  time  with  a  proper 
proportion  of  water,  the  solution  filtered,  and  the  concentrated  filtrate 
examined  in  the  manner  above  described.  Should  an  alkaline  car- 
bonate or  a  carbonate  of  lime  or  magnesia  have  been  administered 
as  an  antidote,  the  whole  of  the  acid  may  be  in  the  form  of  a  nitrate 
of  one  of  these  bases,  and  the  mixture  have  a  neutral  reaction.  In 
case  the  potash  or  soda  antidote  was  employed,  the  examination  is 
conducted  as  before  for  the  separation  of  the  alkaline  nitrate ;  but 
when  the  lime  or  magnesia  antidote  was  administered,  the  concen- 
trated filtered  solution  is  treated  with  potassium  or  sodium  carbonate 
as  long  as  it  produces  a  precipitate,  whereby  the  base  of  the  earthy 
nitrate  will  be  converted  into  an  insoluble  carbonate,  while  the  acid 
will  be  changed  into  an  alkaline  nitrate.  This  mixture  is  then  heated 
for  some  minutes  to  cause  the  complete  subsidence  of  the  insoluble 
carbonate,  and  the  solution  filtered,  after  which  the  filtrate  is  concen- 
trated and  the  nitrate  separated  in  its  crystalline  state. 

From  organic  fabrics. — Stains  produced  by  this  acid  on  articles 
of  clothing  and  like  substances  have  usually  at  first  a  more  or  less 
yellow  color,  then  become  reddish,  and  after  a  time  yellowish-brown. 
The  presence  of  the  acid  may  be  determined  by  boiling  the  stained 
portion  of  the  article  in  a  very  small  quantity  of  pure  water,  filter- 
ing, and  concentrating  the  filtrate,  when,  if  even  only  a  minute 
quantity  of  the  acid  is  present,  the  liquid  will  have  an  acid  reaction. 
The  solution  is  then  tested  in  the  usual  manner.     Instead  of  boiling 


QUANTITATIVE    ANALYSIS.  137 

the  stained  substance  with  pure  water,  it  may  l)e  boih.'d  with  a  very 
dihite  solution  of  potassium  or  sodium  carbonate,  tlie  acid  being 
thus  at  once  converted  into  the  form  of  a  nitrate.  As  nitric  acid  is 
volatile  and  more  readily  dec'omposed  than  sulphuric  acid,  it  much 
more  readily  disap[)ears  from  stained  articles  of  clothing.  Never- 
theless, Dr.  Christison  detected  it  in  stains  on  cloth  after  tlie  lapse 
of  seven  weeks;  and  Dr.  Guy  quotes  an  instance  in  which  it  was 
recovered  under  similar  circumstances  after  an  interval  of  some 
months. 

The  yellow  stains  produced  by  nitric  acid  on  the  skin  after 
a  time  assume  a  brownish-yellow  color.  When  these  spots  are 
moistened  with  a  solution  of  caustic  potash,  they  immediately  ac- 
quire a  bright  orange  hue,  wherein  they  differ  from  somewhat  sim- 
ilar stains  occasioned  by  iodine  and  bromine,  which,  at  least  when 
recent,  on  the  application  of  the  alkali  immediately  disappear. 

Quantitative  Analysis. — There  is  no  ready  method  of  esti- 
mating the  amount  of  nitric  acid  when  in  solution  with  other 
substances.  If  the  liquid  be  simply  a  diluted  solution  of  the  acid, 
the  quantity  of  the  latter  may  be  estimated  sufficiently  near  for 
most  purposes  from  the  specific  gravity  of  the  fluid.  When  the 
acid  exists  in  its  free  state  and  the  solution  contains  no  other  acid 
(except  sulphuric),  its  exact  quantity  may  be  determined  as  follows. 
The  solution  is  treated  with  very  slight  excess  of  baryta  water,  and 
slowly  evaporated  to  dryness  :  during  the  evaporation  the  excess  of 
baryta  added  will  absorb  carbonic  acid  from  the  atmosphere  and 
become  changed  into  barium  carbonate,  which  is  insoluble  in  water. 
The  dry  residue  is  then  treated  with  a  sufficient  quantity  of  pure 
water,  and  the  solution  filtered.  The  filtrate,  which  now  contains 
the  whole  of  the  nitric  acid  in  the  form  of  barium  nitrate,  is  treated 
with  diluted  sulphuric  acid  as  long  as  a  precipitate  is  produced ;  the 
sulphate  of  barium  thus  thrown  down  is  collected  on  a  filter,  washed, 
dried,  and  weighed.  Every  one  hundred  parts  by  weight  of  sul- 
phate of  barium  thus  obtained  correspond  to  54  parts  of  monohy- 
drated  nitric  acid,  or  77.2  parts  of  acid  of  specific  gravity  1.424, 
every  81  grains  of  the  latter  of  which  measure  about  one  fluid- 
drachm. 

If  during  the  investigation  the  acid  has  been  converted  into 
potassium  nitrate,  this  is  transformed  into  the  sulphate  by  treating 


138  HYDEOCHLOEIC   ACID. 

the  concentrated  solution  with  sufficient  sulphuric  acid.  The  mix- 
ture is  then  cautiously  evaporated  to  dryness,  and  the  residue  heated 
to  dull  redness,  when  the  nitric  acid  will  be  entirely  expelled  and 
leave  for  each  equivalent  one  equivalent  of  neutral  sulphate  of 
potassium.  If  the  residue  on  cooling  be  not  entirely  neutral  in  its 
reaction,  it  is  moistened  with  a  little  acid  carbonate  of  ammonium 
solution  and  again  heated.  Every  one  hundred  parts  by  weight  of 
this  salt  correspond  to  72.4  parts  of  monohydrated  nitric  acid. 

Section  III. — Hydrochloric  Acid. 

HydroGhloric  or  muriatic  acid,  formerly  called  spirit  of  salt,  as 
found  in  commerce,  is  a  more  or  less  yellow,  powerfully  acid  liquid, 
which  evolves  irritating  fumes  when  exposed  to  the  air.  But  few 
cases  of  poisoning  by  this  substance  are  reported,  and,  among  these, 
only  perhaps  in  two  instances  was  it  criminally  administered.  In 
its  action  upon  the  tissues  it  is  somewhat  less  corrosive  than  either 
of  the  acids  already  considered. 

Symptoms. — The  symptoms  produced  by  hydrochloric  acid  are 
very  similar  to  those  observed  in  poisoning  by  sulphuric  acid.  When 
the  acid  is  swallowed  in  its  concentrated  state,  the  patient  immediately 
experiences  an  intense  burning  sensation  throughout  the  parts  with 
which  the  liquid  comes  in  contact,  attended  with  a  sense  of  suifoca- 
tion  and  the  eructation  of  gaseous  matters.  These  effects  are  usually 
sooner  or  later  succeeded  by  violent  vomiting,  great  restlessness,  in- 
tense pain  in  the  stomach,  coldness  of  the  extremities,  and  a  small, 
frequent  pulse.  At  first  the  tongue  and  throat  usually  present  a 
white  appearance;  in  a  few  instances,  white  fumes  were  observed  to 
escape  from  the  mouth  soon  after  the  poison  had  been  taken.  In 
some  instances,  on  account  of  the  great  soreness  of  the  throat  and 
swollen  condition  of  the  neighboring  parts,  there  is  great  difficulty 
of  swallowing.  The  bowels  usually  become  obstinately  constipated, 
and  the  urine  scanty  or  entirely  suppressed. 

Dr.  Ogle  briefly  relates  the  following  case  {St.  George's  Hosp. 
Rep.,  iii.  239).  A  man,  aged  twenty-fiv^e,  swallowed  two  ounces  of 
hydrochloric  acid,  and  when  seen  two  hours  later,  he  having  vomited 
some  dark-green  matter  which  eflervesced  on  the  addition  of  sodium 
carbonate,  his  skin  was  warm,  pulse  58,  and  small ;  the  tongue  was 
dry  and  excoriated.  Later  on,  he  complained  of  great  soreness  of  the 
throat  and  fauces,  with  pain  at  the  epigastrium,  and  difficulty  of 


IMIYSIOLOGICAL    EFFECTS.  139 

swallowliifj.  In  spito  oi'  troatmont,  the  pationt  sank,  and  died  on  tlie 
ninth  day. 

In  a  case  cited  l)y  ( )ifila  {Toxicologic ,  1852,  i.  105),  in  which  a 
man  had  administered  to  him  by  mistake  ul)ont  one  ounce  and 
a  half  of  liydrochloric  acid,  there  was  extreme  agitation,  with  a  hot 
and  dry  skin,  small  aii<l  hard  pulse,  fiery-red  tongue,  blackneas  of 
the  lips,  hiccough,  repeated  efforts  to  vomit,  and  intense  pain  in  the 
stomach.  These  symptoms  were  followed  by  vomiting  of  yellow 
matters,  cold  and  clammy  skin,  increased  j)ain,  extremely  frequent 
pulse,  and  continuous  delirium,  and  death  within  about  twenty  hours 
after  the  j)oison  had  been  taken. 

In  a  singular  case  quoted  by  Dr.  Christison  {On  Poisons,  148),  a 
man,  with  suicidal  intent,  swallowed  a  quantity  of  the  acid,  and 
exhibited  no  signs  of  uneasiness  for  some  time  afterward  ;  he  then, 
however,  suddenly  became  faint  and  fell  down.  In  al)out  three  hours 
after  the  acid  had  been  taken  magnesia  and  milk  were  administered, 
but  without  relief.  He  suffered  intense  thirst,  complained  of  exces- 
sive pain  in  the  throat  and  stomach,  and  died  in  about  fifteen  hours. 

If  the  patient  quickly  swallows  the  acid,  it  may  have  little  or  no 
action  upon  the  tissues  of  the  mouth.  Thus,  in  a  case  recently 
reported  by  Dr.  MacDonald,  in  which  a  man  had  swallowed  an 
ounce  and  a  half  of  hydrochloric  acid,  there  was  found  no  corrosion 
of  the  raucous  membrane  either  of  the  mouth  or  fauces.  {Edin.  Med. 
Jour.,  Jnne,  1881,  1093.)  Under  the  prompt  administration  of  anti- 
dotes the  patient  in  this  case  soon  entirely  recovered. 

Period  when  Fatal. — Most  of  the  recorded  cases  of  poisoning  by 
hydrochloric  acid  were  followed  by  death.  The  most  rapidly  fatal 
case  yet  recorded  is,  perhaps,  that  mentioned  by  Dr.  Christison,  in 
which  two  ounces  of  an  equal  mixture  of  strong  hydrochloric  acid 
and  tincture  of  steel  (muriated  tincture  of  iron?)  caused  death  in 
five  hours  and  a  half.  Vomiting  occurred  soon  after  the  mixture 
was  taken,  but  subsequently  ceased.  Although  the  patient  retained 
her  consciousness  until  the  time  of  death,  she  made  no  complaint 
either  of  heat  or  pain  anywhere,  or  of  thirst ;  but  the  pulse  was 
imperceptible,  and  the  muscles  of  the  extremities  contracted.  In 
three  other  instances,  two  of  which  have  already  been  cited,  death 
took  place  in  fifteen,  eighteen,  and  about  twenty  hours,  resj>ectively. 
But  a  case  has  already  been  mentioned  in  which  a  dose  of  two  ounces 
did  not  prove  fatal  until  after  a  period  of  eight  days.     And  two  in- 


140  HYDROCHLORIC   ACID. 

stances  are  recorded  in  which  death  did  not  occur  until  eight  weeks 
had  elapsed.     (Orfila,  Toxicol.,  i.  221 ;  and  Taylor  on  Poisons,  291.) 

Fatal  Quantity. — In  a  case  reported  by  Dr.  Budd,  half  a  fluid- 
ounce  of  the  acid,  taken  with  suicidal  intent,  proved  fatal  in  eighteen 
hours  to  a  woman  aged  sixty-three  years.  {Lancet,  July,  1859,  59.) 
This  seems  to  be  the  smallest  fatal  dose  yet  recorded.  In  this  case 
the  following  symptoms  were  observed  :  vomiting,  collapse,  whiten- 
ing and  abrasion  of  the  lips,  mouth,  and  fauces ;  also,  swelling  of 
the  throat  and  inability  to  swallow,  with  stridulous  breathing  and 
thick  inarticulate  voice,  and  intense  epigastric  pain.  Death,  without 
loss  of  consciousness  until  near  the  last,  took  place  by  exhaustion. 

On  the  other  hand,  Dr.  Toothaker  reports  a  case  in  which  a  man 
recovered  after  having  taken,  by  mistake,  one  ounce  of  officinal  muri- 
atic acid.  It  was  immediately  succeeded  by  violent  burning  of  the 
mouth  and  fauces,  a  sense  of  suffocation,  and  spasms.  After  the 
administration  of  olive  oil,  followed  by  a  mixture  of  milk  and  cal- 
cined magnesia,  copious  vomiting  ensued.  The  strength  of  the 
patient  became  greatly  reduced,  and  the  extremities  so  cold  as  to  re- 
quire the  application  of  sinapisms.  The  next  day  there  was  pain 
and  costiveness,  but  these  were  relieved  by  a  dose  of  castor  oil.  After 
this,  the  patient  very  gradually  recovered.  [Boston  Med.  and  Surg. 
Jour.,  XV.  270.) 

The  following  case  of  recovery  is  reported  by  Dr.  Stevenson 
(Guy's  Hosp.  Rep.,  xiv.  270).  A  man  drank  half  a  wineglassful  of 
strong  hydrochloric  acid,  supposing  it  to  be  brandy.  When  taken 
to  the  hospital  very  soon  after,  the  patient  was  almost  asphyxiated, 
foamed  at  the  mouth,  and  breathed  with  great  difficulty.  The  mouth 
and  fauces  were  clogged  with  tough,  viscid  mucus,  and  the  tongue 
and  adjacent  parts  appeared  excoriated.  His  speech  was  thick  and 
indistinct ;  he  complained  of  great  dryness  of  the  mouth  and  fauces, 
and  of  a  severe  burning  pain  in  the  throat,  more  particularly  in  the 
stomach.  Vomiting  had  occurred  several  times  on  his  way  to  the 
hospital.  Olive  oil  was  administered,  and  then  several  raw  eggs,  the 
latter  with  much  relief.  The  next  day  only  slight  signs  of  the  local 
action  of  the  acid  were  visible  about  the  mouth  and  lips;  but  he 
experienced  great  thirst,  with  a  burning  pain  in  the  throat.  Six  days 
after  taking  the  acid  the  pain  in  the  throat  had  much  diminished, 
and  the  next  day  the  patient  was  discharged  nearly  well.  In  another 
case  recovery  took  place  after  about  a  quarter  of  an  ordinary  tumbler- 


CIIKMICAI.    I'ROl'KllTlKS.  Ill 

fill  of  tlie  commercijil  acid  luul  l)oen  tuki-n  at  a  drau^dit  by  a  woman. 
In  this  instance  the  lips,  month,  and  t()ni.aie  \v(!re  deprived  of  their 
epithelinm,  red,  and  inflamed;  tlie  iances  and  throat  were  mneh 
swollen,  and  upon  the  velum  and  pharynx  there  was  an  exudation 
closely  resemblini!;  the  false  mend)rane  of  diphtheria. 

Treatment. — The  proper  chemical  antidote  is  either  chalk  or 
calcined  magnesia,  or  a  dilute  solution  of  an  alkaline  carbonate.  If 
neither  of  these  substances  be  at  hand,  milk,  white  of  egg,  oil,  or 
demulcents  of  any  kind  should  be  freely  administered.  In  every 
respect  the  treatment  is  the  same  as  in   sulphuric  acid   poisoning 

{ante,  101). 

Post-mortem  Appearances. — In  acute  cases,  the  mucous  mem- 
brane of  the  mouth,  throat,  and  oesophagus  is  usually  more  or  less 
softened,  and  of  a  whitish  or  brownish  color.  The  lining  membrane 
of  the  stomach  is  generally  highly  inflamed,  softened,  and  readily 
separated.  In  the  case  cited  above  which  proved  fatal  in  five  hours 
and  a  half,  the  lower  portion  of  the  oesophagus  had  the  appearance 
of  being  charred.  The  mucous  membrane  of  the  stomach  jiresented 
black  elevated  ridges,  as  if  charred,  while  the  intervening  furrows 
were  of  a  scarlet-red  color;  similar  appearances  were  observed  in 
the  duodenum  and  jejunum.  In  Dr.  Budd's  case,  the  mucous  mem- 
brane of  the  mouth,  fauces,  and  larynx  was  whitened  and  softened, 
the  soft  palate  and  tonsils  were  swollen,  and  a  portion  of  the  lining 
membrane  of  the  larynx  was  entirely  removed.  In  this  case,  the 
local  action  of  the  poison  was  chiefly  confined  to  the  parts  just 
mentioned. 

In  the  case  cited  by  Orfila  which  did  not  prove  fatal  until 
after  a  period  of  eight  weeks,  the  lining  membrane  of  the  throat 
and  oesophagus  was  thickened  and  in  a  state  of  suppuration.  The 
stomach  was  entirely  disorganized,  softened,  and  presented  several 
round  perforations  having  thickened  and  inflamed  edges;  the  py- 
loric orifice  was  thickened  and  contracted.  In  the  small  intestines, 
the  mucous  membrane  throughout  its  extent  was  thickened,  injected 
in  patches,  and  of  an  arborescent  appearance  ;  the  large  intestines 
were  healthy,  and  contained  a  brownish,  fetid  liquid. 

Chemical  Properties. 
General  Chemical  Nature. — Anhydrous  hydrochloric  acid 
is  a  gaseous  compound  of  hydrogen   and   chlorine,  HCl.     It  is  a 


142 


HYDROCHLORIC    ACID. 


colorless,  powerfully  suifoeating  gas,  having  a  density  of  1.26  ; 
when  it  comes  in  contact  with  the  air  it  produces  white  fumes, 
due  to  its  strong  affinity  for  water. 

Hydrochloric  acid,  or  muriatic  acid  of  the  shops,  is  an  aqueous 
solution  of  the  gaseous  compound,  of  which,  according  to  Davy, 
water  at  a  temperature  of  4.5°  C.  (40°  F.)  will  absorb  480  times 
its  volume,  increasing  both  in  volume  and  in  density.  Such  a 
solution  has  a  specific  gravity  of  1.21,  and  contains  nearly  43  per 
cent,  of  anhydrous  acid.  The  solution  is  colorless,  has  a  highly 
irritating  odor,  and  yields  dense  white  fumes  when  a  rod  moist- 
ened with  ammonia  is  presented  to  it.  If  the  solution  be  heated, 
a  portion  of  the  anhydrous  acid  is  readily  expelled  in  the  form  of 
vapor. 

The  following  table,  according  to  E.  Davy,  exhibits  the  per- 
centage by  weight  of  the  anhydrous  acid  in  pure  aqueous  solutions 
of  different  specific  gravities : 


STRE^TQTH    OF    AQUEOUS    SOLUTIONS    OF    HYDROCHLORIC    ACID. 


Sp.  Ge. 

1  Percentage  of 

Sp.  Gr. 

Percentage  op 

Sp.  Gk. 

Percentage  of 

HCl. 

HCl. 

HCl. 

1.21 

42.43 

1.14 

28.28 

1.07 

14.14 

1.20 

40.80 

1.13 

26.26 

1.06 

12.12 

1.19 

1        38.38 

1.12 

24.24 

1.05 

10.10 

1.18 

:        36.36 

1.11 

22.22 

1.04 

8.08 

1.17 

1        34.34 

1.10 

20.20 

1.03 

6.06        1 

1.16 

32.32 

1.09 

18.18 

1.02 

4.04        ! 

1.15 

30.30 

!                                     ; 

1.08 

16.16 

1 

1.01 

2.02 

Hydrochloric  acid  as  found  in  the  shops  has  usually  a  density 
of  about  1.15,  and  a  more  or  less  yellow  color,  due  to  the  presence 
of  free  chlorine  gas  or  chloride  of  iron,  or  both.  It  is  also  liable  to 
be  contaminated  with  sulphuric  and  sulphurous  acids,  arsenic,  nitric 
acid,  and  some  of  the  lower  oxides  of  nitrogen,  lead,  and  common 
salt ;  occasionally  other  impurities  are  present. 

Liquid  hydrochloric  acid  is  readily  decomposed  by  iron,  zinc, 
and  the  stronger  electro-positive  metals,  with  the  formation  of  a 
chloride  of  the  metal  and  the  evolution  of  hydrogen  gas.  But  it  is 
unacted  upon  by  metallic  copper,  even  at  the  boiling  temperature : 
in  this  respect  it  differs  from  nitric  and  sulphuric  acids.  It  is  readily 
decomposed  by  the  basic  metallic  oxides  and  their  carbonates,  with 


SPECIAL,   CHEMICAL    PROPERTII-IS.  1  to 

the  Ibnnati^)!!  of  a  cliloride  ami  water,  and,  in  tlie  case  of  a  carbonate, 
the  evolution  of  carbonic  acid. 

The  mils  resulting  from  this  acid,  or  chlorides  as  they  are  termed, 
are  mostly  colorless,  and,  with  tiie  exception  of  tiie  chlorides  of 
silver  and  lead  and  mercurous  chloride,  are  freely  soluble  in  water. 
Wlu-n  heated  with  diluted  sulphuric  acid,  the  soluble  chlorides,  to- 
gether with  w\ater,  are  readily  decomposed,  giving  rise  to  a  sul- 
phate and  evolving  hydrochloric  acid  gas;  tjjus  :  2NaCl  +  H2SO^  = 
Na2SO,-l-2HCl. 

Special  Chemical  Properties. — When  hydrochloric  acid  is 
heated  with  black  oxide  of  manganese,  both  compounds  undergo  de- 
composition with  the  formation  of  the  chloride  of  the  metal  and  the 
evolution  of  free  chlorine ;  thus:  MnOo+ 4HCl  =  2H20+ MnClg 
-j-Clo.  The  presence  of  the  eliminated  chlorine  maybe  recognized 
by  its"  peculiar  odor,  its  bleaching  properties,  and,  if  not  in  too  minute 
quantity,  its  greenish-yellow  color.  Its  bleaching  property  is  readily 
determined  by  exposing  to  it  a  slip  of  moistened  litmus-paper,  or 
a  slip  of  paper  moistened  with  a  solution  of  indigo;  if  a  slip  of 
Btarch-paper  be  moistened  with  a  solution  of  iodide  of  potassium 
and  exposed  to  the  gas,  it  immediately  acquires  an  intense  blue  color, 
which  after  a  time,  under  the  continued  action  of  the  gas,  is  partially 
or  wholly  discharged.  If  the  evolved  gas  be  brought  in  contact  with 
a  drop  of  a  solution  of  nitrate  of  silver,  or  be  conducted  into  a 
solution  of  this  salt,  it  produces  in  the  first  instance  a  white  film, 
and  in  the  second  a  white  precipitate,  of  chloride  of  silver,  having 
the  properties  to  be  presently  described. 

When  a  soluble  chloride  is  mixed  with  black  oxide  of  manganese 
and  heated  with  sulphuric  acid,  previously  diluted  with  about  an 
equal  volume  of  water,  the  whole  of  the  chlorine  is  eliminated  in  its 
free  state.  The  reactions  in  this  case,  taking  chloride  of  sodium 
as  the  type,  are  as  follows:  2XaCl -f  MnO.+2H.SO,  =  MnSO,+ 
Na,SO/-^  2HoO  -f  CI,.  The  presence  of  the  evolved  chlorine  may 
be  determined  by  the  methods  just  indicated.  If  this  decomposition 
be  conducted  in  a  thin  watch-glass  covered  by  an  inverted  glass 
containing  slips  of  the  moistened  test-papers,  the  fractional  part  of 
a  grain  of  the  salt  will  yield  satisfactory  results. 

Since  the  compounds  resulting  from  hydrochloric  acid  are,  with 
very  few  exceptions,  freely  soluble  in  water,  there  are  but  few  re- 
agents that  precipitate  it  from  solution.     In  the  following  investiga- 


144  HYDEOCHLORIC   ACID. 

tions  in  regard  to  the  behavior  of  solutions  of  hydrochloric  acid, 
pure  aqueous  solutions  of  the  free  acid  were  chiefly  employed.  The 
fractions  indicate  the  amount  of  the  anhydrous  acid  in  solution  in 
one  grain  of  liquid,  and  the  results,  the  behavior  of  one  grain  of  the 

solution. 

1.  Silver  Nitrate. 

IS^itrate  of  silver  throws  down  from  solutions  of  hydrochloric 
acid,  of  chlorides,  and  of  free  chlorine  a  white  amorphous  precip- 
itate of  chloride  of  silver,  AgCl,  which  is  readily  soluble  in  ammo- 
nia, but  insoluble  in  nitric  and  sulphuric  acids ;  it  is  also  readily 
soluble  in  cyanide  of  potassium,  but  insoluble  in  the  fixed  caustic 
alkalies.  When  exposed  to  light,  chloride  of  silver  soon  acquires 
a  purple  color ;  on  the  application  of  heat,  it  readily  fuses,  without 
decomposition,  to  a  yellowish  liquid,  which  on  cooling  solidifies  to  a 
hard,  compact,  nearly  colorless  mass. 

1.  yi-g-  grain  of  anhydrous  hydrochloric  acid,  in  one  grain  of  water, 

yields  a  very  copious,  curdy  precipitate, 

2.  Y^oT  gi'^iii  •  luuch  the  same  results  as  1. 

3.  xo'.'ooT  gi'ain  yields  a  very  good  flocculent  precipitate.     The  solur 

tion  strongly  reddens  litmus-paper. 

4.  5-o,Toir  gi'ain  :  a  very  satisfactory  deposit.     The  solution,  after  a 

time,  slightly  reddens  litmus-paper. 

5.  T-Q-o-iWo"  g^^^'ii  •  i^  ^  fsw  moments,  a  distinct  cloudiness,  which 

soon  becomes  well  marked. 

6.  -5-0-0/roT  grain  yields,  after  a  little  time,  a  slight  opalescence. 

Nitrate  of  silver  also  produces  in  solutions  of  hydrocyanic  acid, 
even  when  strongly  acidulated,  a  white  precipitate  of  cyanide  of 
silver,  which,  like  the  corresponding  chlorine  compound,  is  soluble 
in  ammonia  (although  less  freely),  and  insoluble  in  nitric  acid.  But 
the  cyanide  of  silver,  when  dried  and  heated  in  a  reduction-tube, 
readily  undergoes  decomposition,  with  the  evolution  of  an  inflamma- 
ble gas,  in  which  respects  it  differs  from  the  chlorine  salt.  A  more 
ready  method  of  distinguishing  between  these  acids  is  to  treat  a 
portion  of  the  suspected  solution  with  the  mercury  reagent  described 
below. 

In  neutral  solutions,  nitrate  of  silver  produces  precipitates  with 
several  other  acids  or  elements.  All  of  these  precipitates,  however, 
except  that  from  hydrocyanic  acid,  unlike  the  chloride  of  silver,  are 
readily  soluble  in  nitric  acid,  at  least  in  its  concentrated  state.     So, 


SPECIAL   CHEMICAL    PROPERTIES.  145 

again,  the  rea<;('nt  is  readily  decomposed,  with  the  production  of  a 
white  precipitate,  by  a  great  variety  of  organic  substances ;  these  pre- 
cipitates, however,  like  those  just  mentioned,  are  soluble  in  nitric  acid. 
The  chlorine  may  be  recovered  in  a  soluble  form  from  the  chloride 
of  silver,  by  fusing  the  latter  with  a  mixture  of  sodium  and  potassium 
carbonates,  when  the  chlorine  will  be  transformed  into  an  alkaline 
chloride,  readily  soluble  in  water. 

2.  3Iercurous  Nitrate. 

This  reagent  produces  in  solutions  of  free  hydrochloric  acid  and 
of  chlorides  a  white  amorphous  precipitate  of  mercurous  chloride, 
or  calomel,  HgjClg,  which  is  insoluble  in  concentrated  nitric  acid. 
The  precipitate  is  readily  decomposed  by  the  caustic  alkalies,  with 
the  formation  of  a  black  compound  of  mercury. 

1.  _l_  grain  of  the  anhydrous  acid  yields  a  very  copious  precipitate. 

2.  YW^  grain  yields  much  the  same  results  as  1. 

3.  Yo-.Vuir  grain  :  a  quite  good  precipitate. 

4.  ^u-.Vdit  grain  :  a  very  satisfactory  deposit. 

5.  ToiLTDTr  grain  yields,  after  a  little  time,  a  very  distinct  turbidity. 

]\Iercurous  nitrate  also  produces  white  precipitates  in  solutions 
of  several  other  substances.  When  the  reagent  is  added  to  a  solu- 
tion of  free  hydrocyanic  acid,  as  well  as  of  a  cyanide,  one-half  of 
the  mercury  is  thrown  down  in  its  finely  divided  state  as  a  dark- 
grav  precipitate,  while  the  other  portion  remains  in  solution  in  the 
form  of  cyanide  of  mercury.  This  reaction,  as  intimated  above, 
readily  serves  to  distinguish  between  hydrochloric  and  hydrocyanic 
acids,  as  well  as  between  their  salts. 

3.  Lead  Acetate. 

Acetate  of  lead  produces  in  solutions  of  hydrochloric  acid  and  of 
its  salts,  when  not  too  dilute,  a  white  precipitate  of  chloride  of  lead, 
PbCL,  which  is  somewhat  less  soluble  in  diluted  nitric  acid  than  in 
pure  water.  The  precipitate  is  rather  freely  soluble  in  boiling  water, 
from  which  on  cooling  it  separates  in  its  crystalline  state. 

1.  Yw^  grain  of  hydrochloric  acid,  when  treated  with  the  reagent, 

crystals  immediately  begin  to  separate,  and  in  a  little  time  there 
is  a  quite  good  crystalline  deposit,  Plate  III.,  fig.  1. 

2.  "2^  grain :  on  agitating  the  mixture  with  a  glass  rod,  it  yields, 

10 


146  HYDEOCHLORIC  ACID. 

after  a  few  minutes,  some  few  crystals  of  chloride  of  lead,  which 

are  chiefly  confined  to  the  margin  of  the  drop. 
Acetate  of  lead  also  produces  white  precipitate — usually,  how- 
ever, amorphous — in  solutions  of  several  other  acids,  especially  if 
the  mixture  be  neutral.  Moreover,  the  reagent  is  readily  decomposed 
by  various  organic  substances,  with  the  production  of  a  white  amor- 
phous precipitate. 

Separation  from  Organic  Mixtures. 

Suspected  Solutions. — If  the  solution  has  a  strong  acid  reaction, 
and  is  tolerably  free  from  organic  matter,  a  small  portion  of  the 
liquid  may  be  treated  with  a  few  drops  of  a  strong  solution  of  nitrate 
of  silver.  If  this  produces  a  white  precipitate,  which  when  washed 
in  diluted  nitric  acid  is  insoluble  in  the  stronger  acid,  there  is  little 
doubt  of  the  presence  of  chlorine.  If  this  examination  indicates  the 
presence  of  chlorine,  it  then  becomes  necessary,  even  should  the  solu- 
tion have  a  strong  acid  reaction,  to  determine  whether  it  existed  in 
the  form  of  free  hydrochloric  acid  or  as  a  chloride.  For  this  pur- 
pose, a  portion  of  the  solution  is  evaporated  to  dryness  and  gently 
ignited,  when  if  it  leaves  no  saline  residue  it  is  quite  certain  that 
the  acid  was  uncombined.  Should,  however,  it  leave  such  a  residue, 
this  is  dissolved  in  water  and  tested  for  chlorine.  If  this  element 
be  absent,  it  is  most  probable  that  the  acid  was  free :  however,  a 
mixture  of  a  chloride,  as  common  salt,  and  excess  of  sulphuric  acid 
would,  as  heretofore  pointed  out  in  the  consideration  of  the  re- 
covery of  sulphuric  acid,  yield  upon  evaporation  a  residue  entirely 
free  from  chlorine.  Whether  these  conditions  really  existed  could 
be  readily  determined  by  treating  a  portion  of  the  suspected  solution 
with  chloride  of  barium,  when  if  it  failed  to  yield  a  precipitate,  or 
gave  one  readily  soluble  in  nitric  acid,  the  absence  of  sulphuric  acid 
would  be  fully  established. 

Should  the  suspected  liquid  on  evaporation  leave  a  residue  con- 
taining a  chloride,  it  then  becomes  necessary  to  ascertain  whether  the 
whole  of  the  hydrochloric  acid  may  have  existed  in  that  form.  To 
effect  this,  a  given  portion  of  the  liquid  is  neutralized  by  pure  sodium 
carbonate,  evaporated  to  dryness,  the  incinerated  residue  dissolved  in 
water  containing  a  little  nitric  acid,  the  chlorine  precipitated  by  nitrate 
of  silver,  and  the  precipitate  collected,  washed,  dried,  and  weighed : 
an  equal  volume  of  the  liquid,  without  the  addition  of  carbonate  of 


SEPARATION    FROM   ORGANIC   MIXTURES.  147 

sodium,  is  then  evaporated  to  dryness,  the  residue  incinerated,  and 
tlie  chlorine  precipitated,  as  in  the  previous  operation,  by  nitrate  oi' 
silver.  It'  the  weight  of  the  precipitate  obtained  by  the  former  of 
these  methods  exceed  the  weiglit  of  that  obtained  by  the  latter,  then 
a  portion  of  the  acid  existed  in  its  free  state :  the  exact  quantity  of 
the  acid  thus  present  may,  of  course,  be  readily  deduced  from  tiie 
ditference  thus  observed. 

For  the  separation  of  free  hydrochloric  acid  from  complex  mix- 
tures containing  organic  solids,  it  has  been  proposed  to  heat  the  mix- 
ture, after  the  addition  of  water  if  necessary,  to  near  the  boiling 
temperature,  then  filter,  and  distil  the  filtrate  at  a  gentle  heat  to  the 
consistency  of  a  thin  syrup,  the  distillate  being  collected  in  a  proper 
receiver.  The  liquid  thus  collected  is  then  examined  by  the  silver 
test.  As,  however,  hydrochloric  acid  strongly  adheres  to  organic 
matter,  none  of  the  acid,  unless  present  in  comparatively  large  quan- 
tity, may  pass  over  into  the  receiver.  Under  these  circumstances, 
Orfila  recommended  to  treat  the  residue  in  the  retort  with  a  solution 
of  tannin,  filter,  and  then  distil  the  filtrate,  as  before,  to  near  dryness. 
From  w^hat  has  already  been  stated,  it  is  obvious  that  if  the  mixture 
thus  distilled  contained  a  chloride  and  free  sulphuric  acid,  it  would 
give  rise  to  hydrochloric  acid,  which  would  appear  in  the  distillate. 
This  objection  could,  of  course,  be  answered  by  testing  a  portion  of 
the  residue  with  chloride  of  barium. 

Contents  of  the  Stomach. — Any  solids  present  are  cut  into  small 
pieces,  and  the  mass,  after  dilution  with  distilled  water  if  necessary, 
kept  at  near  the  boiling  temperature  for  half  an  hour  or  longer, 
then  strained,  the  strained  liquid  filtered,  and  then  submitted  to  the 
process  of  distillation  described  above.  If,  however,  an  alkaline  or 
earthy  antidote  has  been  administered,  and  the  mixture  has  a  neutral 
reaction,  then  a  given  portion  of  the  filtered  liquid  is  evaporated  to 
dryness,  the  incinerated  residue  dissolved  in  water,  and  any  chlorine 
present  estimated  in  the  form  of  chloride  of  silver.  In  these  investi- 
gations it  must  be  borne  in  mind  that  the  gastric  juice  contains  not 
only  alkaline  chlorides,  but  also,  it  is  said,  free  hydrochloric  acid ; 
and,  moreover,  that  common  salt,  or  chloride  of  sodium,  is  almost 
universally  present,  at  least  in  minute  quantity,  in  articles  of  food. 
The  gastric  juice,  however,  according  to  most  observers,  normally 
contains  only  the  merest  trace  of  the  free  acid ;  but  the  chlorides 
exist  in  very  notable  quantity. 


148  HYDROCHLORIC   ACID. 

From  the  facts  just  stated,  it  is  obvious  that  the  detection  of  a 
mere  trace  of  free  hydrochloric  acid,  or  of  a  chloride  in  minute  quan- 
tity, would  not  in  itself  be  any  evidence  of  poisoning  by  this  acid. 
If  it  be  shown  that  the  base  of  the  chloride  present  corresponds  to 
that  of  the  antidote  alleged  to  have  been  administered,  this  fact  may 
materially  assist  in  forming  an  opinion  as  to  the  true  nature  of  the 
case.  When  the  whole  of  the  acid  has  been  converted  into  a  chloride 
by  the  administration  of  an  antidote,  it  may  be  recovered  in  its  free 
state  by  first  evaporating  the  mixture  to  dryness,  then  distilling  the 
incinerated  residue  with  strong  sulphuric  acid,  and  collecting  the 
evolved  acid  in  a  small  quantity  of  water  contained  in  a  well-cooled 
receiver. 

For  the  detection  of  free  hydrochloric  acid  in  the  contents  of  the 
stomach,  L.  Bouis  advises  {Ann.  d'Hyg.,  1874,  i.  457)  to  add  a  small 
quantity  of  binoxide  of  manganese,  and  gently  heat  the  mixture, 
when  any  hydrochloric  acid  present,  but  not  common  salt  or  a  chloride, 
will  evolve  free  chlorine,  which  may  be  recognized  by  its  bluing 
action  upon  paper  moistened  with  a  solution  of  potassium  iodide  and 
starch  paste.  Or,  the  suspected  contents  may  be  heated  with  a  little 
nitre,  when  any  free  hydrochloric  acid  present  will  give  rise  to  aqua 
regia,  while  with  common  salt  or  a  chloride  no  such  change  will  take 
place.  The  presence  of  any  aqua  regia  thus  formed  may  be  deter- 
mined by  its  solvent  action  upon  gold-leaf,  and  from  the  amount  of 
gold  dissolved  the  amount  of  free  hydrochloric  acid  can  be  calculated. 
By  the  latter  method,  L.  Bouis  states  that  he  recognized  a  few  centi- 
grammes of  hydrochloric  acid  in  the  presence  of  a  large  quantity  of 
liquid. 

From  organic  fabrics. — Stains  produced  by  hydrochloric  acid  on 
articles  of  clothing,  and  like  substances,  may  be  examined  by  gently 
boiling  the  stained  portion  with  pure  water  for  some  minutes,  and 
testing  the  filtered  liquid  in  regard  to  its  reaction  upon  litmus-paper, 
and  with  a  solution  of  nitrate  of  silver.  When  chlorine  is  thus  dis- 
covered, it  should  be  determined,  in  the  manner  already  pointed  out, 
whether  it  exists  in  the  form  of  the  free  acid  or  simply  as  a  chloride. 
As  hydrochloric  acid  is  volatile,  it  sooner  or  later  entirely  disappears 
from  stains  of  this  kind. 

Quantitative  Analysis. — The  quantity  of  free  hydrochloric 
acid,  or  its  equivalent  in  the  form  of  a  soluble  chloride,  is  most 


QUANTITATIVK    ANALYSIS.  ]  iU 

readily  determined  by  precipitating  it  as  chloride  of  silver.  The 
solution  is  treated  with  a  solution  of  silver  nitrate  as  long  as  it  yields 
a  precipitate,  and  the  niixtiire  gently  heated  until  the  whole  of  the 
precipitate  has  deposited  ;  the  precipitate  is  then  collected  on  a  small 
filter,  thoroughly  washed,  dried,  and  weighed.  Every  one  hundred 
parts,  by  weight,  of  chloride  of  silver  thus  obtained  correspond  to 
25.43  parts  of  anhydrous  hydrochloric  acid,  or  about  81  parts  of 
liquid  acid  of  specific  gravity  1.15;  one  fluid-drachm  of  the  latter 
acid  weighs  about  sixty-five  and  a  half  grains. 


150  OXALIC   ACID. 


CHAPTER    III 

OXALIC   ACID,   HYDKOCYANIC   ACID,   PHOSPHORUS. 

Section  I. — Oxalic  Acid. 

History. — Oxalic  acid,  in  its  crystalline  state,  is  an  organic  com- 
pound of  the  elements  carbon,  hydrogen,  and  oxygen,  combined 
with  water,  its  composition  being  C2H204,2H20.  It  is  found  in  the 
common  rhubarb-plant,  wood-sorrel,  and  several  other  plants,  and 
is  occasionally  met  with  in  human  urine,  only,  however,  as  an  ab- 
normal product.  For  commercial  purposes  it  is  usually  obtained  by 
the  action  of  nitric  acid  upon  starch  or  sugar.  In  its  uncombined 
state  it  is  a  white  crystalline  solid,  having  an  intensely  acid  taste. 
From  its  close  resemblance  to  sulphate  of  magnesium,  or  Epsom  salt, 
it  has  on  several  occasions  been  fatally  mistaken  for  that  substance. 
Either  alone,  or  in  combination  in  a  soluble  form,  it  is  a  powerful 
poison,  and  has  in  several  instances  been  administered  as  such ;  but 
it  has  much  more  frequently  been  taken  for  the  purpose  of  self- 
destruction. 

Symptoms. — The  symptoms  produced  by  oxalic  acid  depend 
not  only  on  the  quantity  taken,  but  also,  somewhat,  on  the  degree 
of  concentration  under  which  it  exists.  When  swallowed  in  large 
quantity  and  in  a  concentrated  state,  it  produces  an  immediate  burn- 
ing pain  in  the  mouth  and  throat,  succeeded  by  vomiting  and  intense 
pain  in  the  stomach,  and,  as  the  case  advances,  great  muscular  pros- 
tration, with  hurried  respiration,  pale  and  anxious  countenance,  cold 
and  clammy  skin,  small  and  feeble  pulse,  and,  in  some  instances, 
delirium  and  convulsions.  The  vomited  matters  have  not  unfre- 
quently  contained  blood. 

When  the  dose  is  not  large  or  is  much  diluted,  nothing  more 
than  a  strongly  acid  taste  may  be  experienced  in  the  mouth  and 
throat,  and  the  pain  in  the  stomach,  as  well  as  the  vomiting,  may  be 


PHYSIOLOGICAL   EFFECTS.  161 

imu'h  ilehivcd.  Although  early  and  continuous  vomiting  is  a  com- 
mon symptom,  yet  it  has  in  some  cases  been  entirely  absent.  In 
a  case  quoted  by  Dr.  Christison,  a  man  swallowed  half  an  ounce  of 
the  i)()ison,  dissolved  in  ten  parts  of  water,  without  experiencing  any 
p;iiii  in  the  abdomen  for  six  hours,  and  there  was  no  vomiting  for 
seven  hours,  except  when  emetics  were  administered.  In  most  of 
the  instances  in  which  no  vomiting  occurred,  tiie  dose  was  either 
small  or  greatly  diluted;  but  this  symptom  has  been  absent  when 
the  jioison  was  taken  in  large  (quantity  and  in  a  concentrated  state. 

A  man,  aged  twenty-one  years,  swallowed  with  suicidal  intent 
about  an  ounce  of  the  poison.  He  instantly  felt  a  burning  sensation 
in  the  mouth,  throat,  and  oesophagus,  and  intense  pain  in  the  stomach. 
He  soon  vomited,  and  when  taken  to  the  hospital  complained  of  a  burn- 
ing sensation  along  the  course  of  the  oesophagus  and  in  the  stomach ; 
there  were  lividity  of  the  face  and  extremities,  relaxation  of  the  mus- 
cles, and  the  surface  was  cold  and  clammy ;  the  heart's  action  was 
irregular,  and  the  sounds  somewhat  distant;  respiration  was  natural; 
pulse  extremely  feeble  ;  tongue  large,  oedematous,  and  covered  with 
thick,  woolly  fur;  conjunctivae  dusky;  pupils  natural.  An  emetic 
removed  from  the  stomach  a  large  quantity  of  green-looking  fluid. 
After  a  time  the  patient  appeared  much  better,  and  continued  to  im- 
prove until  the  fifth  day,  when  he  arose  to  relieve  his  bowels,  and 
died  almost  immediately.  {Lancet,  Nov.  1860,  509.)  In  another 
case,  a  woman,  aged  twenty  years,  to  destroy  herself  took  a  quantity 
of  oxalic  acid,  and  died  from  its  effects  within  about  twenty  minutes. 

In  a  protracted  case  reported  by  Dr.  C.  T.  Jackson  {Boston 
Med.  and  Surg.  Jour.,  xxx.  17),  the  following  symptoms  were  ob- 
served. A  man,  aged  thirty  years,  took  in  solution  about  one  ounce 
of  crystallized  oxalic  acid,  mistaking  it  for  Epsom  salt.  He  imme- 
diately perceived,  by  the  strong  acid  taste  and  burning  sensation 
in  the  throat,  that  he  had  made  a  mistake,  and  he  drank  a  large 
quantity  of  warm  water  to  excite  vomiting,  which  produced  the 
desired  effect.  He  also  took,  by  the  advice  of  a  physician,  ipecacu- 
anha and  antimony  in  emetic  doses,  and  castor  oil.  The  matter  first 
vomited  was  of  a  dark  chocolate  color.  In  twelve  hours  after  the 
occurrence  the  patient  was  in  a  state  of  complete  prostration  :  face, 
lips,  throat,  and  tongue  swollen  and  livid ;  pulse  almost  extinct, 
fluttering  and  irregular;  heart  in  a  continual  fluttering  palpitation; 
great  jactitation  and  distress ;  with  incessant  vomiting.     The  matter 


152  OXALIC   ACID. 

vomited  was  a  thick,  grumous,  and  jelly-like  fluid,  of  a  yellow  color, 
mixed  with  white  flocculi.  He  complained  of  no  pain  at  the  epigas- 
trium, or  over  the  bowels,  on  pressure.  Carbonate  of  lime  was  now 
administered,  but  rejected.  On  the  second  day  the  face  was  tumid, 
and  of  a  livid  color;  tongue  swollen  and  livid;  pulse  130;  and  the 
urine  entirely  suppressed.  The  vomiting  continued  for  two  or  three 
days,  with  great  distress  and  anxiety ;  the  tongue  became  covered 
with  a  brown  coating,  the  tip  of  the  organ  being  red  and  dry ;  and 
there  was  great  thirst,  but  no  pain.  On  the  sixth  day  his  mind 
began  to  wander,  and  petechise  appeared  on  the  face,  chest,  and  other 
parts  of  the  body,  which  appeared  as  if  sprinkled  with  blood.  He 
continued  to  fail,  and  died  on  the  tenth  day  after  the  poison  had  been 
taken.  In  several  of  the  reported  cases  there  was  great  irritability 
of  the  bowels,  with  frequent  purging,  and  the  discharged  matters  in 
some  instances  contained  blood. 

Oxalic  acid  is  equally  poisonous  in  the  form  of  an  alkaline  oxalate 
as  when  taken  in  its  free  state.  A  woman  swallowed  some  of  the 
acid  oxalate  of  potassium.  In  two  or  three  minutes  she  threw  up 
her  arms  and  fell  down  insensible.  In  half  an  hour  an  emetic  was 
given,  but  without  inducing  vomiting.  Half  an  hour  later  she  had 
partially  recovered  consciousness.  The  mucous  membrane  of  the 
mouth  and  pharynx  was  injected,  and  the  tonsils  were  enlarged,  but 
there  was  no  loss  of  membrane.  Chalk  mixture  was  administered, 
and  afterward  vomiting  was  induced.  The  next  day  she  complained 
of  slight  tenderness  of  the  abdomen,  and  soreness  of  the  throat  and 
mouth,  and  there  were  some  slight  excoriations  on  the  inner  side  of 
the  lips.  Two  days  later  the  patient  was  discharged  as  convalescent. 
{Ghiy's  Hosp.  Rep.,  1874,  416.) 

Period  when  fatal. — Much  the  larger  proportion  of  the  recorded 
cases  of  poisoning  by  oxalic  acid  proved  fatal ;  and  among  these, 
death  in  most  instances,  perhaps,  occurred  in  less  than  an  hour  after 
the  poison  had  been  taken.  In  a  case  quoted  by  Dr.  Taylor,  an 
unknown  quantity  of  the  poison  caused  death  in  about  three  min- 
utes. {On  Poisons,  312.)  Dr.  Christison  refers  to  two  cases  which 
proved  fatal  in  about  ten  minutes ;  and  in  another,  death  ensued  in 
from  fifteen  to  twenty  minutes.  In  a  case  mentioned  by  Dr.  Pereira, 
death  occurred  in  twenty  minutes.  Death  also  occurred  within  a 
similar  period  in  an  instance  in  which  the  patient  vomited  almost 
immediately  after  the  poison  had  been  taken.     In  an  instance  in 


FATAL     QUANTITY.  153 

which  the  taUint:;  of  tliree-quarters  of  an  ounce  of  oxalic  acid  was 
quickly  folh)wecl  by  voinitin^r,  and  death  in  about  ten  minutes,  only 
two  grains  of  the  poison  were  ibund  in  the  stomach  after  death. 

The  fatal  period  luus,  however,  been  delayed  for  many  hours,  and 
even  days.  Two  instances  are  reported  in  which  death  did  not  occur 
until  thirteen  hours  had  elapsed ;  and  another,  in  which  it  was 
delayed  until  the  fifth  day.  In  Dr.  Jackson's  case,  already  men- 
tioned, life  was  prolonged  until  the  tenth  day.  The  most  protracted 
case  yet  recorded  is,  perhaps,  that  mentioned  by  Dr.  Beck  {Med. 
Jur.,  ii.  499),  in  which  a  woman  died  from  the  secondary  effects  of 
the  poison  after  a  period  of  some  months. 

Fatal  Quantity. — The  effects  of  given  quantities  of  oxalic  acid, 
like  those  of  most  other  poisons,  have  been  far  from  uniform.  In 
one  of  the  cases  just  referred  to,  that  proved  fatal  in  thirteen  hours, 
half  an  ounce  of  the  poison,  largely  diluted  with  water,  had  been 
taken.  Dr.  Taylor  quotes  a  case  in  which  a  boy,  aged  sixteen  years, 
ate  about  one  drachm  of  the  solid  acid,  and  it  proved  fatal  within 
nine  hours ;  and  another,  in  which  a  woman,  aged  twenty-eight  years, 
swallowed  three  drachms  of  the  crystallized  acid,  and  was  found  dead 
in  one  hour  afterward.  These  are  the  smallest  fatal  doses  yet  re- 
ported. Serious  symptoms,  however,  have  followed  the  taking  of 
much  smaller  quantities  of  the  poison.  In  a  case  reported  by  Dr. 
Babington,  two  scruples  of  the  acid,  taken  in  combination  with  car- 
bonate of  sodium,  caused  severe  symptoms,  from  which  the  patient 
did  not  entirely  recover  until  some  weeks  afterward. 

On  the  other  hand,  complete  recovery  has  taken  place  after  very 
large  quantities  of  oxalic  acid  had  been  taken.  Not  less  than  six 
instances  of  this  kind  are  reported,  in  each  of  which  half  an  ounce 
of  the  acid  had  been  swallowed  :  in  most  of  these,  however,  early 
treatment  was  employed.  A  like  result  has  also  been  observed  in 
several  instances  in  which  an  ounce  of  the  poison  had  been  taken. 
In  a  singular  case  quoted  by  Wharton  and  Stille  {3Ied.  Jur.,  496),  a 
woman  dissolved  two  large  tablespoonfuls  of  oxalic  acid,  by  mistake 
for  Epsom  salt,  in  a  small  quantity  of  water,  and  took  it  on  an  empty 
stomach.  Some  twenty  minutes  afterward  she  vomited,  at  first  the 
solution  she  had  taken,  and  then  a  dark-colored,  bloody  fluid,  in  which 
were  numerous  white  flakes.  Ipecacuanha  and  afterward  prepared 
chalk  were  administered,  and  in  about  an  hour  she  was  found  quiet 
and  nearly  free  from  the  intense  burning  pain  in  her  stomach  and 


154  ■      OXALIC    ACID. 

throat.    She  subsequently  vomited  again,  and  matters  similar  to  those 

vomited  were  discharged  from  the  bowels  by  purging.  Soon  after 
this  she  entirely  recovered.  If  this  case  is  correctly  reported,  the 
quantity  of  the  poison  taken  was  about  one  ounce  and  a  quarter. 

Teeatmext. — Powdered  chalk,  magnesia,  or  its  carbonate,  sus- 
pended in  water  or  milk,  or  a  solution  of  the  acid  carbonate  of  mag- 
nesium, should  be  administered  as  speedily  as  possible.  Either  of 
these  substances  will  completely  neutralize  oxalic  acid,  with  the  ])ro- 
duction  of  an  insoluble  compound.  After  thus  neutralizing  the 
poison,  if  there  is  not  free  vomiting,  an  emetic  should  be  admin- 
istered. Large  draughts  of  warm  water  may  be  given  to  aid  the 
vomiting.  One  or  other  of  these  chemical  antidotes  has  in  several 
instances  been  employed  with  great  advantage.  When,  however,  the 
symptoms  have  once  fully  manifested  themselves,  they  usually  ter- 
minate fatally  in  spite  of  any  treatment. 

If  neither  of  these  earthy  compounds  is  at  hand,  an  emetic  should 
be  given,  and  its  exhibition  followed  by  large  quantities  of  tepid 
^vater.  The  stomach-pump  may  sometimes  be  employed  with  advan- 
tage. As  the  alkaline  carbonates  form  with  the  acid  soluble  poison- 
ous salts,  they  will  not  serve  as  antidotes  in  this  kind  of  poisoning. 

Post-mortem  Appearaxces. — These  are  subject  to  considerable 
variation.  In  rapidly  fatal  cases,  the  mucous  membrane  of  the 
mouth  and  throat  is  generally  more  or  less  disorganized,  and  of  a 
white  appearance.  The  lining  membrane  of  the  oesophagus  is  some- 
times much  softened,  and  easily  detached,  and  the  blood-vessels 
congested  with  dark  blood.  The  stomach  has  been  found  much 
contracted  in  size,  and  its  external  coat  highly  inflamed.  The  con- 
tents of  this  organ  are  usually  thick,  highly  acid,  and  of  a  dark 
color,  due  to  the  presence  of  altered  blood.  The  mucous  membrane 
is  pale  or  of  a  brownish  color,  injected,  softened,  and  sometimes 
corrugated.  In  a  few  instances  the  coats  of  the  stomach  presented 
a  dark  or  nearly  black  appearance ;  and  they  have  been  so  much 
softened  as  to  be  lacerated  by  the  slightest  pressure.  In  a  case 
mentioned  by  Dr.  Christison,  the  coats  of  the  stomach  were  perfo- 
rated. The  small  intestines  have  in  several  instances  shown  signs 
of  irritation ;  and  the  liver  and  spleen  have  been  found  in  a  highly 
congested  state.  In  this  connection,  it  is  important  to  bear  in  mind 
that  oxalic  acid,  even  when  taken  in  large  quantity,  has  in  some  few 
instances  destroyed  life  without  leaving  any  well-marked   morbid 


GENERAL  CHEMICAL  NATURE.  155 

changes,  or  in  fact  any  ahiiunnal  appearance  whatever,  in  the  dead 
body.  In  a  case  suddenly  fatal  on  the  fourth  day  after  a  quantity 
of  oxalic  acid  had  been  taken,  the  walls  of  the  stomach  wca'c  found 
somewhat  congested,  and  the  organ  contained  a  (juantity  of  bloody 
fluid  ;  otherwise  it  was  natural. 

In  a  case  in  which  an  ounce  of  oxalic  acid  had  been  taken  by  a 
man,  on  an  empty  stomach,  and  proved  fatal  under  continued  vomit- 
ing and  purging  in  twenty-jive  minutes,  on  inspection  the  brain,  heart, 
lungs,  and  kidneys  were  found  healthy.  The  mucous  membrane  of 
the  stomach  was  found  highly  congested,  and  curiously  corrugated, 
as  if  the  muscular  coat  had  been  irritated  and  contracted.  No  ulcer- 
ation or  softening  was  observed.     [Lancet,  Dec.  1860,  593.) 

In  a  case  which  proved  fatal  in  thirteen  hours,  the  lining  mem- 
brane of  the  throat  and  oesophagus  presented  an  appearance  similar 
to  that  of  having  been  scalded,  and  could  be  easily  separated.  The 
stomach  contained  a  pint  of  thick,  dark-colored  fluid  ;  and  its 
mucous  coat  was  pulpy,  in  many  points  black,  and  in  others  highly 
inflamed ;  its  outer  coat  was  also  inflamed.  Similar  appearances, 
but  in  a  less  degree,  were  observed  both  externally  and  internally  in 
the  small  intestines.  The  lining  membrane  of  the  trachea  was  also 
very  red. 

In  the  protracted  case  reported  by  Dr.  Jackson,  the  stomach 
contained  a  yellow  fluid,  and  was  remarkably  corrugated ;  its  mu- 
cous membrane  was  much  thickened,  soft,  of  a  bright  red  color,  and 
contained  numerous  small  ulcers.  The  lining  membrane  of  the 
duodenum  was  also  thickened,  red,  and  studded  with  ulcers ;  and 
that  of  the  other  portions  of  the  small  intestines  congested.  The 
large  intestines,  and  other  abdominal  organs,  were  healthy.  The 
heart  was  empty,  except  a  small  quantity  of  blood  in  the  right  side. 
In  a  case  that  proved  fatal  on  the  twenty-third  day,  the  lining 
membrane  of  the  oesophagus  and  stomach  was  completely  destroyed, 
and  in  places  entirely  removed ;  and  the  muscular  coat,  throughout 
the  gullet  and  stomach,  was  much  thickened,  highly  injected,  and 
presented  a  dark  appearance. 

Chemical  Properties. 

General  Chemical  Nature. — Oxalic  acid,  when  pure,  forms 
colorless,  transparent,  odorless,  four-sided  crystalline  prisms,  which 
contain  two  molecules  of  water  of  crystallization,  C2H204,2Aq.     It 


156  OXALIC  ACID. 

is  the  strongest  of  the  vegetable  acids.  The  crystals  are  perma- 
nent at  ordinary  temperatures ;  but  when  ex})osed  to  warm  air,  they 
part  with  their  water  of  crystallization  and  become  opaque. 

Oxalic  acid  is  readily  soluble  in  water  at  ordinary  temperatures. 
The  extent  to  which  the  acid  dissolves  in  this  fluid  has  been  variously 
stated  at  from  eight  to  fifteen  times  its  weight  of  the  liquid.  And, 
in  fact,  either  of  these  extremes  will  equally  express  its  solubility, 
unless  some  exact  temperature  be  specified.  As  the  mean  result  of 
three  very  closely  accordant  experiments,  we  have  foimd  that  when 
excess  of  the  pure  crystallized  acid  is  kept  in  contact  with  pure 
water  for  five  hours  at  a  temperature  of  15.5°  C.  (60°  F.),  and  the 
solution  then  filtered,  the  filtrate  contains  one  part  of  the  acid  in  9.5 
parts  of  water.  It  is  more  freely  soluble  in  warm  water ;  and  boil- 
ing water,  it  is  said,  will  take  up  its  own  weight  of  the  acid.  Berze- 
lius  met  with  a  sample  of  the  crystallized  acid  which  was  so  strongly 
impregnated  with  nitric  acid,  used  in  its  preparation,  that  it  required 
only  two  parts  of  cold  water  for  solution.  The  pure  acid  is  also 
freely  soluble  in  alcohol,  but  insoluble  in  ether,  and  very  sparingly 
soluble  in  chloroform.  When  one  grain  of  the  pure  crystallized 
acid  is  dissolved  in  one  hundred  grains  of  w^ater,  and  the  solution 
violently  agitated,  for  a  few  moments,  with  an  equal  volume  of  pure 
chloroform,  this  liquid  extracts  one-twentieth  of  a  grain  of  the  acid. 

The  oxalates,  or  salts  of  this  acid,  are  usually  colorless  and 
crystallizable,  and  for  the  most  part,  except  those  of  the  alkalies, 
insoluble  in  water.  They  are  all  decomposed  by  heat,  the  acid 
being  resolved  into  carbonic  acid  and  carbonic  oxide. 

Special  Chemical  Properties. — Oxalic  acid,  when  pure,  is 
entirely  dissipated  at  a  temperature  of  about  177°  C.  (350°  F.).  In 
this  respect  it  diifers  from  the  sulphate  of  magnesium,  which  it 
closely  resembles  in  appearance,  and  which  leaves  a  fixed  residue, 
even  at  high  temperatures.  When  the  acid  is  heated  with  strong 
sulphuric  acid,  it  is  resolved,  without  charring,  into  carbonic  acid 
and  carbonic  oxide  gases,  which  escape :  tartaric  and  other  organic 
acids  when  thus  heated  are  speedily  charred.  Solutions  of  the  acid 
have  a  strongly  acid  taste  and  reaction,  even  when  much  diluted,  and 
fail  to  be  precipitated  by  the  alkaline  carbonates :  a  solution  of  Epsom 
salt  has  a  bitter  taste,  is  neutral  in  its  reaction,  and  yields  a  white 
precipitate  when  treated  with  sodium  carbonate. 

Pure  aqueous  solutions  of  oxalic  acid,  when  slowly  evaporated  to 


SPECIAL    CHEMICAL    PROPERTIES.  157 

dryness,  leave  the  acid  in  the  form  of  long  crystalline  priBnis.  When 
one  o;rain  of  a  l-l()()th  .solution  of  the  acid  is  allowed  to  evaporate 
spontaneously,  it  leaves  a  comparatively  large  mass  of  crystals  ;  when 
the  solution  contains  the  1-lOOOth  of  its  weight  of  the  acid,  it  yields 
a  quite  good  deposit,  the  crystals  having  the  forms  represented  in 
Plate  III.,  fig.  2;  the  l-10,000th  of  a  grain  of  the  acid,  under 
similar  circumstances,  yields  a  very  satisfactory  deposit  of  small 
prisms  and  cross  lets. 

In  the  followino;  details  in  regard  to  the  behavior  of  solutions  of 
oxalic  acid,  the  fractions  indicate  the  fractional  part  of  a  grain  of  the 
pure  crystallized  acid  in  solution  in  one  grain  of  water;  and  the 
results  refer  to  the  reactions  of  one  grain  of  the  solution. 

1.  Silver  Nitrate. 

Solutions  of  free  oxalic  acid,  and  of  its  alkaline  salts,  yield  with 
nitrate  of  silver  a  white  amorphous  precipitate  of  oxalate  of  silver, 
^?,2^2^ii  which  is  slowly  soluble  in  cold  nitric  acid,  but  readily 
soluble  in  the  heated  acid;  it  is  also  readily  soluble  in  solutions  of 
ammonia,  but  insoluble  in  concentrated  solutions  of  acetic,  tartaric, 
and  oxalic  acids.  When  the  dried  precipitate  is  heated  on  platinum 
foil,  it  is  decomposed  and  dissipated  in  slightly  detonating  puffs, 
being  resolved  into  metallic  silver  and  carbonic  acid  gas;  thus: 
AgAA=Ag2+2C02. 

1.  YW^  grain  of  oxalic  acid,  in  one  grain   of  water,  yields  a  very 

copious  precipitate,  which,  in  the  mixture,  requires  about  three 
drops  of  strong  nitric  acid  for  complete  solution.  When  dried 
and  heated,  it  is  dissipated  in  the  manner  peculiar  to  this  salt. 

2.  ydVo  g'ain  yields  a  rather  copious  precipitate,  which,  when  dried 

and  heated,  is  rapidly  dissipated,  but  not  in  distinct  puffs. 

3.  x"(5-Voir  g'^'^in  :  a  very  good  deposit. 

4.  -j-g-.Vrro  gi'ain  yields  an  immediate  turbidity,  and,  in  a  very  short 

time,  a  quite  satisfactory  deposit. 

5.  YuiKoiro  grain:  an  immediate  opalescence,  and,  after  a  little  time, 

a  quite  distinct  deposit. 

6.  3-0-^,15-oir  g^ain  yields,  after  some  minutes,  a  distinct  cloudiness. 

Fallacies. — Nitrate  of  silver  is  also  readily  decomposed,  with  the 
production  of  a  white  precipitate,  by  a  great  variety  of  organic 
principles.  And  it  also  produces  similar  precipitates  with  several 
other  acids,  especially  from  neutral   solutions.     Thus,  it  occasions 


158  OXALIC   ACID. 

precipitates  in  neutral  solutions  of  the  carbonates,  tartrates,  phos- 
phates, borates,  citrates,  chlorides,  and  cyanides,  and  also,  in  most 
instances,  with  the  free  acids  of  these  salts.  All  these  precipitates, 
however,  except  those  from  the  chlorides,  cyanides,  and  their  free 
acids,  are  soluble  in  acetic  acid,  in  which  respect  they  diifer  from 
the  oxalate  of  silver.  So,  also,  the  chloride  and  cyanide  of  silver — 
produced  by  the  reagent  from  solutions  of  chlorides  and  cyanides 
or  their  free  acids — are  readily  distinguished  from  the  oxalic  acid 
precipitate,  in  that  they  are  insoluble  in  nitric  acid.  Moreover,  the 
chloride  of  silver,  when  dried  and  heated,  quietly  fuses  without 
decomposition ;  and  the  cyanide,  under  similar  circumstances,  is 
decomposed  with  the  production  of  a  fixed  residue  and  the  evolution 
of  an  inflammable  gas.  The  precipitates  produced  from  the  car- 
bonates, tartrates,  phosphates,  borates,  and  citrates,  when  dried  and 
heated,  also,  unlike  the  oxalic  acid  deposit,  leave  a  fixed  residue. 

2.   Calcium  Sulphate. 

Sulphate  of  calcium  throws  down  from  solutions  of  free  oxalic 
acid,  and  of  soluble  oxalates,  a  white  granular  precipitate  of  oxalate 
of  calcium,  CaC20^,2Aq,  which  is  readily  soluble  in  nitric  and 
hydrochloric  acids,  but  insoluble,  or  very  nearly  so,  in  acetic  and 
other  vegetable  acids.  As  sulphate  of  calcium  is  soluble  only  to  a 
limited  extent  in  water,  its  solution  does  not  precipitate  the  whole 
of  the  oxalic  acid  from  somewhat  concentrated  solutions,  unless  the 
reagent  solution  be  added  in  very  large  quantity.  From  such  solu- 
tions the  whole  of  the  acid  may  be  readily  precipitated,  as  calcium 
oxalate,  by  employing  as  the  reagent  a  solution  of  chloride  of  calcium 
or  any  of  the  other  more  soluble  salts  of  lime. 

1.  yl^  grain  of  free  oxalic  acid  yields  with  a  drop  of  the  calcium 

sulphate  solution  a  very  good,  granular  precipitate.  A  small 
drop  of  chloride  of  calcium  solution  produces  a  much  more 
copious  deposit,  which  is  in  the  form  of  small  rectangular  and 
notched  plates,  somewhat  larger  than  the  granules  produced  by 
the  sulphate  of  calcium. 

2.  Y^oT  g^'ai"  •    ar"  immediate  cloudiness,  and  soon  a  quite  good 

granular  deposit.  Chloride  of  calcium  produces  much  the  same 
reactions,  but  the  precipitate  consists  chiefly  of  small  plates  and 
octahedral  crystals,  which  vary  in  size  from  the  l-3000th  to  the 
l-7000th  of  an  inch,  Plate  III.,  fig.  3.     The  precipitate  oc- 


SPECIAL    CHEMICAL    PROPERTIES.  159 

ciisioned  by  the  sulplmte  of  calciiini  is  in  tin;  lonii  ol"  <iv:il 
granules,  wliicli  uniformly  measure  about  tlie  l-10,000tli  of 
an  inch  in  their  lonj^est  diameter. 

3.  y^l5-jpj5-  tj;rain  :  very  soon  a  perceptible  cloudiness,  and  in  a  little 

time  a  quite  satisfactory  deposit. 

4.  Tyj- 'ij-jj-g-  grain  yields,  after  a  little  time,  a  quite  distinct  turbidity, 

5.  ^-o-.Voo"  gi"^i"  •  after  some  minutes,  a  just  perceptible  opalescence. 

Fallacies. — The  reaction  of  this  reagent  is  much  less  open  to 
fallacy  than  that  of  nitrate  of  silver.  From  neutral  solutions, 
however,  calcium  sul})hate  produces  somewhat  similar  precipitates 
with  the  alkaline  carbonates,  phosphates,  and  borates;  but  from  the 
last-mentioned  only  when  the  solution  is  extremely  concentrated. 
Cliloride  of  calcium  also  occasions  white  precipitates  in  solutions  of 
these  salts,  and,  in  addition,  in  strong  solutions  of  the  alkaline 
citrates.  But  these  precipitates  are  all  readily  soluble  in  acetic  acid, 
and  may  thus  be  distinguished  from  the  calcium  oxalate.  In  this 
connection  it  may  be  remarked  that  even  concentrated  solutions  of 
free  tartaric,  citric,  hydrochloric,  and  hydrocyanic  acids,  and  of  their 
salts,  fail  to  yield  a  precipitate  with  calcium  sulphate.  When,  there- 
fore, this  reagent  and  nitrate  of  silver  produce  in  a  suspected  solu- 
tion white  precipitates,  which  in  both  instances  are  insoluble  in 
acetic  acid,  the  results  are  not  then  open  to  any  of  the  objections 
thus  far  mentioned  under  these  tests  individually. 

Sulphate  of  calcium  also  produces  white  precipitates,  even  in 
acid  solutions  of  lead,  baryta,  and  strontia,  the  sulphates  of  these 
metals  being  thrown  downi.  These  precipitates,  however,  unlike  the 
calcium  oxalate,  are  insoluble  in  nitric  and  hydrochloric  acids ;  they 
are  also  insoluble  in  acetic  acid.  Chloride  of  calcium  fails  to  pre- 
cipitate solutions  of  barium  and  strontium  ;  but  it  causes  in  strong 
solutions  of  salts  of  lead  a  white  precipitate  of  chloride  of  lead, 
which  slowly  disappears  on  the  addition  of  water. 

3.  Barium  ChloHde. 

This  reagent  occasions  in  solutions  of  free  oxalic  acid,  when  not 
too  dilute,  a  white  precipitate  of  oxalate  of  barium,  which  is  readily 
soluble  in  nitric  and  hydrochloric  acids,  but  soluble  with  difficulty  in 
oxalic  acid,  and  still  less  soluble  in  acetic  acid.  As  the  oxalate  of 
barium  is  soluble  in  hydrochloric  acid,  even  when  highly  diluted, 
the  reagent  fails  to  precipitate  the  whole  of  the  oxalic  acid  from 


160  OXALIC    ACID. 

strong  solutions  of  the  free  acid :  since  the  hydrochloric  acid  set  free 
by  the  decomposition  prevents  the  further  action  of  the  reagent. 
The  precipitate  produced  from  strong  solutions  of  the  acid  is  usually 
in  the  form  of  groups  of  bold,  sharp-pointed  crystalline  needles. 
Neutral  solutions  of  the  alkaline  oxalates  yield  with  the  reagent  a 
white  amorphous  precipitate,  which  soon  becomes  crystalline.  This 
reaction  is  very  much  more  delicate  than  when  the  acid  exists  in  its 
free  state. 

1.  YTo   grain   of  free  oxalic  acid  yields  a  quite    good    amorphous 

precipitate,  which  soon  becomes  granular,  and  in  a  little  time 
crystalline,  forming  in  most  instances  bold  dumb-bells  and 
needles,  Plate  III.,  fig.  4.  If  nitrate  of  barium  be  employed 
as  the  reagent,  the  precipitate  is  usually  in  the  form  of  small 
octahedral  crystals. 

2.  YoVo  gi^ain :  after  a  few  moments  the  mixture  becomes  turbid, 

and  in  a  little  time  yields  a  good  deposit  of  crystalline  needles, 
and  granules. 

3.  gQ^QQ  grain  :  on  stirring  the  mixture  with  a  glass  rod,  it  yields, 

after  some  time,  a  quite  distinct  deposit  of  granules  and  needles, 
which  under  the  microscope  are  quite  satisfactory. 
Fallacies. — Chloride  of  barium  also  produces  in  solutions  of  free 
sulphuric  acid  and  of  sulphates  a  white  precipitate  of  sulphate  of 
barium,  which,  however,  differs  from  the  oxalic  acid  precipitate  in 
regard  to  its  form,  and  in  being  insoluble  in  strong  nitric  acid.  In 
neutral  solutions  the  reagent  also  produces  white  precipitates  with 
the  alkaline  carbonates  and  several  other  salts;  but  all  these  deposits, 
except  that  from  sulphates,  are  readily  soluble  in  acetic  acid. 

4.  Strontium  Nitrate. 

Nitrate  of  strontium  throws  down  from  solutions  of  free  ox- 
alic acid  a  white  precipitate  of  oxalate  of  strontium,  which  is  very 
sparingly  soluble  in  acetic  and  oxalic  acids,  but  freely  in  nitric  and 
hydrochloric  acids.  When  the  acid  exists  in  the  form  of  an  alkaline 
oxalate,  the  delicacy  of  the  reaction  of  this  reagent  is  much  increased, 

1.  Ywo  gi"ain  of  the  free  acid  yields  an  immediate  precipitate,  and  in 

a  little  time  there  is  a  very  good  deposit  of  octahedral  crystals, 
plates,  and  small  granules,  Plate  III.,  fig.  5. 

2,  YWoo   grain  >  ^  a  little  time,  granules,  prisms,  and  octahedral 

crystals. 


SPECIAL   CIIKMICAL    IMIOPERTIES.  101 

3.  -jj-^jl^  grain:    in    a   little   time,  a  distinct  turbidity,  and    >ooii   a 

rather  good  granular  precipitate. 

4.  p,yJ|y,Y  grain:  in  a  few  minutes,  a  very  distinct  granular  deposit. 
Tlie  objections  to  the  reactions  of  this  test,  and  the  methods  of 

answering  them,  arc  the  same  as  pointed  out  under  the  preceding 

reagent. 

5.  Lead  Acetate. 

Solutions  of  free  oxalic  acid,  and  of  its  soluble  salts,  yield  with 
this  reagent  a  white  precipitate  of  oxalate  of  lead,  which  is  insoluble 
in  acetic  acid,  but  readily  soluble  in  nitric  acid. 

1 .  .j_i_j.  grain  of  the  free  acid  yields  a  very  copious  precipitate,  con- 

sisting of  a  mass  of  crystalline  needles,  Plate  III.,  fig.  6. 

2.  y^\j-jj  grain  :  a  copious  precipitate,  which  immediately  begins  to 

crystallize. 

3.  g^i^^  grain :  a  good  deposit,  which  soon  becomes  changed  into 

stellate  crystalline  groups. 

4.  yiy.^-oir  gi'^i"  '•  ^^  immediate  turbidity,  and  soon,  stellate  crystals. 

5.  YTJ.'^Wo  grain :  very  soon  the  mixture  becomes  opalescent,  and,  in 

a  little  time,  yields  a  satisfactory  granular  deposit. 

6.  4^,^-^j-jj-  grain :  after  some  time,  the  mixture  becomes  slightly  turbid. 

Fallacies. — Solutions  of  sulphuric  acid  and  of  sulphates,  and 
strong  solutions  of  hydrochloric  acid  and  of  chlorides,  also  yield, 
when  treated  by  the  reagent,  white  precipitates,  which,  however,  are 
insoluble  in  strong  nitric  acid.  The  reagent  also  produces  white 
precipitates  in  neutral  solutions  of  carbonates,  phosphates,  and  sev- 
eral other  salts,  and  also  with  a  great  variety  of  organic  substances. 
These  deposits,  however,  at  least  for  the  most  part,  are  readily 
soluble  in  acetic  acid. 

The  oxalic  acid  may  be  recovered  in  its  free  state  from  the 
oxalate  of  lead  by  suspending  the  latter  in  water  and  passing 
through  the  mixture  a  stream  of  sulphuretted  hydrogen  gas,  as 
long  as  it  causes  any  blackening  of  the  mixture.  By  this  means 
the  oxalate  of  lead  will  be  entirely  decomposed,  the  metal  being 
precipitated  as  black  sulphide  of  lead,  while  the  eliminated  acid  will 
remain  in  solution:  PbCA  4- H,S  =  PbS  +  C2H  A-  On  now 
warming  the  mixture,  to  facilitate  the  deposition  of  the  precipitate 
and  expel  the  excess  of  gas  added,  filtering,  and  concentrating  the 
filtrate  at  a  moderate  temperature,  the  solution  on  cooling,  if  suf- 
ficiently concentrated,  will  deposit  the  acid  in  its  crystalline  form. 

11 


162  OXALIC  ACID. 

The  precipitate  produced  by  the  reagent  from  ten  grains  of  a 
1-lOOOth  solution  of  the  free  acid,  when  washed  and  suspended  in 
ten  grains  of  water,  then  treated  with  sulphuretted  hydrogen,  and 
the  solution  filtered,  will  furnish  ten  grains  of  liquid,  which  when 
examined  in  separate  drops  by  the  preceding  reagents  will  yield 
results  not  to  be  distinguished  from  those  obtained  from  a  1-lOOOth 
solution  of  the  pure  acid.  In  other  words,  the  1-lOOth  of  a  grain 
of  the  acid,  when  in  solution  in  ten  grains  of  water,  may  be  pre- 
cipitated by  acetate  of  lead  and  the  acid  recovered  in  its  free  state, 
without  any  appreciable  loss.  The  presence  of  organic  matter  may, 
however,  considerably  modify  these  results. 

6.   Copper  Sulphate. 

Sulphate  of  copper  produces  in  solutions  of  free  oxalic  acid,  when 
not  too  dilute,  a  precipitate  of  oxalate  of  copper,  having  a  very  light 
bluish  or  greenish  color,  the  tint  depending  on  the  strength  of  the 
Solution.  The  precipitate  is  insoluble  in  acetic  and  oxalic  acids,  and 
dissolves  to  a  very  limited  extent  in  even  large  excess  of  strong  nitric 
acid ;  it  is  also  insoluble  in  salts  of  ammonia,  but  dissolves  readily 
in  the  pure  alkali. 

1.  Y^  grain  yields  a  very  copious  flocculent  precipitate. 

2.  -g-^  grain  :  after  a  little  time,  a  granular  precipitate,  which  for  the 

most  part  floats  on  the  surface  of  the  mixture ;  the  addition  of 
a  few  drops  of  strong  nitric  acid  does  not  cause  the  granules  to 
disappear. 

3.  Y^g-Q  grain  yields,  after  some  time,  a  slight  precipitate,  which  is 

dissolved  on  the  addition  of  a  drop  of  nitric  acid. 
Fallacies. — Sulphate  of  copper  also  produces  precipitates  in  neutral 
solutions  of  carbonates  and  of  phosphates,  and  is  also  decomposed  by 
certain  kinds  of  organic  matter  with  the  production  of  a  precipitate ; 
but  all  these  deposits  are  distinguished  from  the  oxalate  of  copper  in 
being  readily  soluble  in  nitric  and  hydrochloric  acids.  Solutions  of 
free  sulphuric,  hydrochloric,  tartaric,  and  citric  acids,  and  of  their 
salts,  fail  to  be  precipitated  by  this  reagent. 

Separation  from  Organic  Mixtures. 

Suspected  Solutions. — When  the  solution  contains  much  organic 
matter,  none  of  the  preceding  tests  should  be  applied  directly  to  the 
mixture,  since  under  these  conditions  they  are  all  liable  to  produce  a 


SEPARATION    FROM    ORGANIC   MIXTURES.  163 

precipitate,  evou  in  tlio  absence  of  oxalic  acid.  If  tlie  solution  is 
strongly  acid  in  its  reaction  and  contains  mechanically  suspended 
solids,  the  mixture,  properly  diluted  with  water  if  necessary,  is  di- 
gesteil  at  a  moderate  heat  for  fifteen  minutes  or  longer,  then  filtered, 
the  filtrate  concentrated  to  a  small  volume,  and,  if  neceasary,  again 
filtered. 

As  a  preliminary  stej),  a  drop  of  the  liquid  may  now  be  examined 
by  the  sulphate  of  copper  test.  If  this  produces  a  faintly  bluish 
precipitate,  insoluble,  or  nearly  so,  in  nitric  or  hydrochloric  acid, 
there  is  little  doubt  of  the  presence  of  oxalic  acid.  If  the  precipitate 
thus  produced  is  quite  copious,  and  the  liquid  under  examination 
nearly  colorless,  then  the  remaining  portion,  after  further  concentra- 
tion if  thought  best,  is  allowed  to  stand  in  a  cool  place  for  some  hours, 
in  order  that  the  acid,  in  part  at  least,  may  crystallize  out.  Any 
crystals  thus  obtained  are  separated  from  the  liquid,  gently  washed, 
then  dissolved  in  a  small  quantity  of  pure  w'ater,  and  the  solution 
tested  in  the  ordinary  manner.  On  furtiier  concentrating  the  liquid 
from  which  the  crystals  separated,  a  second  crop  may  be  obtained. 
If  the  crystals  deposited  in  these  operations  are  highly  colored,  they 
should  be  redissolved  in  a  little  warm  water  and  purified  by  recrys- 
tallizatiou  before  being  tested. 

Should,  however,  the  preliminary  examination  by  the  copper  test 
indicate  the  presence  of  only  a  minute  quantity  of  the  acid,  or  should 
the  liquid  be  highly  colored,  then  the  remaining  portion  is  treated 
with  slight  excess  of  a  solution  of  acetate  of  lead,  by  which  the  whole 
of  the  acid  will  be  precipitated  as  oxalate  of  lead,  together  with 
more  or  less  organic  matter.  The  precipitate  thus  produced  is  col- 
lected on  a  filter  and  thoroughly  washed,  first  with  water  acidulated 
with  acetic  acid,  then  with  pure  water.  The  moist  precipitate  is 
then  diffused  in  an  appropriate  quantity  of  w-ater  and  exposed  to 
a  stream  of  sulphuretted  hydrogen  gas  until  the  whole  of  the 
white  compound  is  thoroughly  blackened,  which  may  require  an 
hour  or  longer.  By  this  treatment,  as  already  pointed  out,  any 
oxalate  of  lead  present  will  be  decomposed,  the  acid  entering  into 
complete  solution,  and  the  metal  being  thrown  down  as  sulphide. 
The  liquid  is  now  separated  from  the  precipitate  by  filtration,  and 
kept  at  a  moderate  temperature  until  the  odor  of  the  sulphuretted 
gas  has  entirely  disappeared.  It  is  then,  if  colorless,  examined  by 
the  usual  tests;    if,  however,  it  is  highly  colored,  any  oxalic  acid 


164  OXALIC   ACID. 

present  is  purified  by  crystallization,  in  the  manner  above  described, 
and  then  tested. 

The  methods  now  described  would  yield  equal  results  whether 
the  acid  existed  in  its  uncorabined  state  or  in  the  form  of  a  soluble 
oxalate  in  the  original  liquid,  and,  therefore,  do  not  serve  to  dis- 
tinguish the  state  in  which  it  was  present.  This,  however,  in 
medico-legal  investigations,  is  rarely  a  matter  of  much  importance. 
Should  it  be  desired  to  determine  this  point,  it  may  be  approxima- 
tively  done  by  evaporating  the  prepared  filtered  liquid  to  dryness 
on  a  water-bath,  and  extracting  the  residue  with  very  strong  alcohol, 
which  will  dissolve  the  free  acid  if  present  as  such,  together  with 
more  or  less  foreign  matter,  but  only  a  trace  of  an  alkaline  oxalate, 
nearly  the  whole  of  the  latter,  unless  present  in  only  very  minute 
quantity,  remaining  undissolved.  The  filtered  alcoholic  solution 
may  now  be  evaporated  to  dryness  on  a  water-bath,  the  residue 
digested  with  a  small  quantity  of  water,  and  the  filtered  liquid 
examined  by  either  of  the  above-mentioned  methods.  The  residue 
remaining  undissolved  by  the  alcohol,  supposed  to  contain  an  alka- 
line oxalate,  is  stirred  with  distilled  water,  the  solution  filtered,  and 
then  examined  in  the  usual  manner. 

Contents  of  the  Stomach. — If  no  chemical  antidote  has  been 
administered,  the  contents  of  the  stomach  are  collected  in  a  porcelain 
dish,  tested  in  regard  to  their  reaction,  and  the  inside  of  the  organ 
well  washed  with  distilled  water,  the  v^^ashings  being  collected  with 
the  contents  in  the  dish.  The  mixture,  after  the  addition  of  more 
water  if  necessary,  is  heated  to  about  the  boiling-point  for  half  an 
hour  or  longer,  the  cooled  liquid  strained,  the  solids  on  the  strainer 
washed,  and  the  united  liquids  filtered,  then  concentrated  and  again 
filtered.  The  liquid  may  now  either  be  evaporated  to  dryness,  and 
the  residue  thoroughly  extracted  by  strong  alcohol,  as  described 
above  for  suspected  solutions,  or  it  may  be  treated  with  slight  ex- 
cess of  acetate  of  lead,  the  precipitate  collected  on  a  filter,  washed 
with  water  acidulated  with  acetic  acid,  and  any  oxalate  of  lead 
present  subsequently  decomposed  by  sulphuretted  hydrogen  gas. 

Instead  of  decomposing  the  oxalate  of  lead  by  sulphuretted 
hydrogen,  it  has  been  proposed  to  boil  it  for  about  half  an  hour  in 
an  appropriate  quantity  of  highly  diluted  sulphuric  acid,  by  which 
it  will  be  resolved  into  insoluble  sulphate  of  lead  and  free  oxalic 
acid.     The  liquid  is  then  filtered,  exactly  neutralized  by  ammonia, 


SEI'MJATION    FFtOM    OFtGANH'    MIXTURES.  105 

an<]  tested.  Uiulcr  Llieso  circiun.staiiccs,  the  poison  would  exist  its 
oxiilatc  of  aninionia,  mixed  with  more  or  less  sulphate  of  amnio- 
nimii ;  the  latter  being  formed  I'loiu  the  excess  of  sulphuric  acid  crn- 
ployed  in  the  decom|)osition  of  the  oxalate  of  lead.  The  j)resence 
of  this  sulphate  would  not  interfere  with  the  reactions  of  the  silver, 
sulphate  of  cidcium,  and  copper  tests;  but  it  would  yield  with 
the  barium,  strontium,  and  load  reagents  white  precipitates  of  the 
sulphates  of  these  metals.  Of  these  two  methods  of  effecting  the 
decomposition  of  the  oxalate  of  lead,  the  former  is  much  to  be 
preferred. 

Should  lime  or  magnesia  have  been  administered  as  an  antidote, 
the  contents  of  the  stomach,  as  well  as  any  matters  vomited  prior  to 
death,  may  have  a  neutral  reaction,  and  contain  the  ])oison  in  the 
form  of  an  insoluble  oxalate  of  one  or  other  of  these  bases.  Under 
these  circumstances,  the  suspected  matters,  especially  all  earthy 
solids,  are  collected  in  a  dish,  the  mass  made  quite  liquid  by  the 
addition  of  warm  water,  and  thoroughly  stirred ;  any  organic  solids 
present  are  then  washed  in  the  liquid  and  removed,  and  the  remain- 
ing solids  allowed  completely  to  subside.  When  this  has  taken 
place,  the  liquid  is  decanted,  and  the  solids  are  again  washed  with 
fresh  water;  they  are  then  diffused  in  a  small  quantity  of  pure  water, 
a  quantity  of  pure  potassium  carbonate,  somewhat  exceeding  that  of 
the  earthy  matter  present,  is  added,  and  the  mixture  boiled  for  about 
half  an  hour,  the  liquid  evaporated  during  the  operation  being  re- 
l>laced  by  distilled  water.  The  earthy  oxalate  will  now  be  changed 
into  an  insoluble  carbonate,  while  the  oxalic  acid  will  be  in  solu- 
tion in  the  form  of  potassium  oxalate.  This  solution,  after  filtra- 
tion, is  treated  WMth  decided  excess  of  acetic  acid,  and  the  oxalic  acid 
precipitated  by  a  solution  of  acetate  of  lead.  The  precipitate  thus 
produced  is  collected,  washed,  and  decomposed  by  sulphuretted  hydro- 
gen gas  in  the  manner  already  described. 

In  case  of  the  discovery  of  oxalic  acid  in  vomited  matters  or 
the  contents  of  the  stomach,  it  might  be  objected,  in  a  medico-legal 
investigation,  that  the  acid  was  a  normal  constituent  of  certain  vege- 
table structures,  some  of  which  are  sometimes  used  as  articles  of  food 
or  administered  medicinally.  Thus,  it  is  present  in  common  sorrel, 
in  culinary  rhubarb,  or  pie-plant,  and  in  the  rhubarb  of  the  shops. 
In  these  substances,  however,  it  exists  only  in  minute  quantity,  and 
in  its  combined  state,  either  as  oxalate  of  potassium  or  of  calcium. 


166  OXALIC   ACID. 

But  should  even  only  a  minute  quantity  of  the  poison  be  discovered, 
the  symptoms  and  other  circumstances  attending  a  case  of  poisoning 
by  the  acid  would  rarely  leave  any  doubt  wliatever  as  to  its  true 
nature. 

The  Urine. — Oxalic  acid,  when  taken  either  in  its  free  or  com- 
bined state  into  the  stomach,  soon  appears  in  the  urine,  usually  in  the 
form  of  octahedral  crystals  of  calcium  oxalate.  The  forms  of  these 
crvstals  readily  distinguish  them  from  all  other  urinary  deposits ; 
thev  are  very  similar  in  form  to  those  of  the  oxalate  of  strontium, 
as  figured  in  Plate  III.,  iig.  o.  These  crystals  are  often  present  in 
the  urine  at  the  time  it  is  voided,  but  more  frequently  they  do  not 
separate  until  after  some  hours. 

For  the  purpose  of  making  this  examination,  a  small  portion  of 
the  liquid  is  gently  rotated  in  a  watch-glass,  until  the  sediment  col- 
lects at  the  bottom  of  the  fluid,  when  the  clear  liquid  is  decanted ; 
the  sediment  is  then  washed  in  a  similar  manner  with  pure  water, 
which  in  its  turn  is  decanted,  and  the  deposit  examined  by  the  micro- 
scope, under  an  amplification  of  about  one  hundred  and  twenty-five 
diameters.  If  none  of  the  crystals  are  thus  found,  and  the  urine  is 
fresh,  some  ounces  of  it  may  be  allowed  to  stand  quietly  for  several 
hours,  the  clear  liquid  decanted,  and  the  sediment  collected,  washed, 
and  examined  as  before. 

In  this  connection,  it  must  be  borne  in  mind  that  these  crystals 
also  thus  occur  not  only  after  the  ingestion  of  certain  articles  of 
food,  but  not  unfrequently  as  the  result  of  disease,  and  sometimes 
even  without  any  apparent  cause.  In  fact,  we  have  found  the  latter 
to  be  the  case  much  more  frequently  than  seems  to  be  generally 
supposed. 

If  it  be  desired  to  examine  the  urine  for  the  presence  of  the  free 
acid  or  of  a  soluble  oxalate,  the  liquid,  after  the  addition  of  a  little 
acetic  acid,  may  be  evaporated  to  about  one-fourth  its  volume,  filtered 
if  necessary,  the  filtrate  treated  with  slight  excess  of  acetate  of  lead, 
any  precipitate  thus  produced  decomposed  by  sulphuretted  hydrogen, 
and  the  filtered  solution  tested  by  the  usual  reagents. 

QuANTiTATRT'E  ANALYSIS. — From  pure  solutions  oxalic  acid 
may  be  estimated  with  considerable  accuracy  in  the  form  of  oxalate 
of  lead  (PbCaOj.  The  solution  is  treated  with  a  little  pure  acetic 
acid,  and  a  solution  of  acetate  of  lead  added  as  long  as  a  precipitate 


HYDROCYANIC    ACID.  107 

is  produced ;  wlicn  the  precipitate  has  completely  subsided,  it  is 
collected  ou  a  filter  of  known  \vei»jht,  well  washed  with  pure  water, 
dried  at  100°  O.  (212°  F.),  and  weighed.  Everyone  hundred  parts 
l)v  weight  of  oxalate  of  lead  thus  obtained  correspond  to  42.5  parts 
of  crvstalli/.ed  oxalic  acid. 

If  the  acid  has  been  jjrecipitated  as  oxalate  of  calcium,  this  is 
thoroughly  washed  and  dried,  then  exjmsed  for  a  few  minutes  to  a 
very  dull  red  heat.  In  this  last  operation  the  oxalate  will  be  con- 
verted into  calcium  carbonate,  every  one  hundred  parts  of  which 
correspond  to  one  hundred  and  twenty-six  parts  of  the  crystallized 
acid. 

Section  II. — Hydrocyanic  Acid. 

History  and  Composition. — This  substance,  also  known  as  prussic 
acid,  is  a  compound  of  the  organic  radical  cyanogen  (CN)  with  the 
element  hydrogen,  its  composition  being  represented  by  the  formula 
HON  or  HCy.  In  its  pure  state,  hydrocyanic  acid  is  a  colorless, 
volatile  liquid,  having  a  peculiar  odor,  somewhat  resembling  that  of 
bitter  almonds.  It  is  one  of  the  most  powerful  and  rapidly  fatal 
poisons  yet  known ;  and  many  of  its  compounds  are  about  equally 
poisonous.  It  may  be  obtained  from  various  vegetable  substances, 
as  bitter  almonds,  the  kernels  of  peaches,  plums,  apricots,  and  cherries, 
apple-pips,  the  flowers  of  the  peach  and  cherry-laurel,  the  bark  of 
wild  cherry,  and  the  root  of  mountain  ash.  In  many  of  these  sub- 
stances, however,  the  acid  does  not  exist  as  such,  but  is  the  result  of 
the  decomposition  to  which  they  are  subjected  in  its  preparation. 

For  ordinary  purposes,  hydrocyanic  acid  is  usually  obtained  by 
distilling  one  of  its  salts  with  dilute  sulphuric  or  hydrochloric 
acid.  The  acid  of  the  shops  is  a  solution  of  the  anhydrous  acid, 
usually  in  water,  but  sometimes  in  alcohol,  and  varies  in  strength 
from  1  to  25  per  cent.,  according  to  the  directions  of  the  Pharma- 
copoeia followed  for  its  preparation.  The  United  States  Pharma- 
copoeia directs  a  strength  of  2  per  cent,  of  the  pure  acid  ;  and 
about  the  same  proportion  is  directed  by  the  British  Colleges.  The 
preparation  known  as  Scheele's  acid  sometimes  contains  as  much 
as  5  per  cent,  of  real  acid,  but  usually  its  strength  falls  very  short 
of  this.  Of  several  specimens  of  commercial  acid  examined  some 
years  since,  we  found  none  to  contain  over  1.5  per  cent,  of  anhydrous 
acid ;   and  one  of  the  samples,  which  had  not  before  been  opened 


168  HYDEOCYAXIC    ACID. 

after  havino-  left  the  hands  of  the  maniifactiu'er,  did  not  contain  even 
a  trace  of  the  acid. 

An  aqueous  solution  of  hydrocyanic  acid,  especially  when  exposed 
to  the  light,  is  prone  to  undergo  spontaneous  decomposition,  with  the 
formation  of  a  brown  deposit.  This  fact,  in  a  measure  at  least, 
accounts  for  the  difference  observed  in  the  strength  of  samples  of  the 
acid  prepared  after  the  same  formula.  This  decomposition  is  much 
retarded  by  the  presence  of  a  minute  quantity  of  a  mineral  acid,  and 
for  that  purpose  a  trace  of  sulphuric  acid  is  frequently  added  to  the 
solution.  According  to  J.  Williams,  aqueous  solutions,  even  when 
containing  5  per  cent,  of  the  acid,  may  be  preserved  unchanged 
for  long  periods  by  the  addition  of  20  per  cent,  of  glycerin.  An 
aqueous  solution  of  the  acid,  when  pure,  is  perfectly  colorless.  In 
regard  to  its  physiological  effects,  hydrocyanic  acid  belongs  to  the 
class  of  narcotic  poisons. 

Symptoms. — These,  both  in  respect  to  the  time  within  which 
they  appear  and  their  character,  depend  upon  the  quantity  of  the 
acid  taken.  When  taken  in  large  quantity,  it  not  unfrequently 
proves  so  rapidly  fatal  that  no  well-marked  symptoms  are  observed. 
During  the  act  of  swallowing  a  large  dose,  the  patient  experiences 
a  hot  bitter  taste,  and  is  either  immediately  or  at  most  within  a  very 
few  minutes  seized  with  complete  loss  of  muscular  power  and  of 
consciousness.  The  respiration  becomes  hurried,  but  often  convul- 
sive, and  sometimes  stertorous,  the  pulse  imperceptible,  the  extremi- 
ties cold,  the  eyes  prominent,  the  pupils  dilated,  and  in  many  in- 
stances there  are  convulsions. 

In  a  case  reported  by  Hufeland,  in  which  a  man  swallowed  about 
fortv  grains  of  the  pure  acid,  in  the  form  of  an  alcoholic  solution, 
the  patient  immediately  staggered  a  few  steps,  and  then  fell,  appar- 
ently lifeless.  When  seen,  almost  instantly  afterward,  by  a  physician, 
the  pulse  was  imperceptible  and  the  respiration  entirely  suspended. 
After  a  short  interval,  the  man  made  a  very  forcible  expiration ;  the 
extremities  became  cold,  the  eyes  prominent,  glistening,  and  insen- 
sible to  light,  and  after  a  few  convulsive  expirations  he  died,  within 
five  minutes  after  the  poison  had  been  taken. 

The  following  case  was  reported  to  Professor  A.  Stille  by  Mr. 
Clay  Hall.  {Amer.  Jour.  Med.  Sci.,  Jan.  1868,  277.)  A  gentleman 
with  suicidal  intent  took  about  one  hundred  drops  of  diluted  hydro- 
cyanic acid,  purporting  to  contain  2  per  cent,  of  the  anhydrous  acid. 


PHVSI<)I,()(iICAL    KKFKCTS.  Ifi9 

When  seen  by  Mr.  Hall,  williiii  five;  niiniitos  after  taking  the  j)ois()n, 
the  man  was  fbnnd  lying  extended  upon  the  floor,  nnconseious.  His 
muscles  were  relaxed  and  flaccid,  with  the  exception  of"  the  muscles 
of  the  jaw,  this  being  firmly  closed  ;  his  hands  were  folded  acroas 
his  breast,  as  in  repose;  the  eyes  were  fixed,  but  life-like,  the  pupils 
being  normal;  respiration  was  slow,  but  not  labored;  his  pulse  was 
about  50,  becoming  slower  and  less  strong  to  the  moment  of  death  ; 
the  veins  of  the  neck  and  face  were  strongly  congested.  Not  the 
slightest  odor  of  the  acid  could  be  perceived  in  his  expirations ;  nor 
was  any  perspiration  perceptible.  His  respiration  became  slower 
and  slower,  until  intervals  of  over  one  minute  intervened,  and  he 
quietly  died  in  from  fifteen  to  twenty  minutes  after  taking  the 
poison,  the  pupils  dilating  at  the  moment  of  death. 

It  was  formerly  believed  that  when  prussic  acid  was  taken  in 
rapidly  fatal  quantity  it  always  produced  immediate  insensibilitv  ; 
but  this  is  by  no  means  always  the  case.  When  taken  in  such 
quantity,  the  symptoms  usually  appear  within  a  very  few  seconds, 
yet  they  have  in  several  instances  been  delayed  sufficiently  long  for 
the  patient  to  ])erform  a  series  of  voluntary  acts.  In  a  case  related 
by  Dr.  Sewell,  a  man  swallowed  seven  drachms  of  Scheele's  prepara- 
tion of  the  acid,  believed  to  contain  about  twenty-one  grains  of  the 
anhydrous  poison,  after  which  he  walked  to  the  door  of  his  room, 
unlocked  it,  called  for  assistance,  then  walked  to  a  sofa  and  stretched 
himself  upon  it;  in  a  very  little  time  after  this  he  was  found  in  an 
insensible  state,  with  stertorous  breathing,  and  soon  died.  (Boston 
Med.  and  Surg.  Jour.,  xxxvii.  322.) 

The  following  remarkable  case  is  related  by  Mr.  Hickman. 
[Lancet,  1866,  i.  310.)  A  man,  by  mistake  for  some  medicine, 
swallowed  half  an  ounce  of  the  diluted  acid,  containing,  as  was 
afterward  determined,  something  over  three  grains  and  a  half  of  the 
pure  acid.  After  taking  the  dose,  he  ran  up-stairs  to  the  house- 
surgeon,  traversing  a  distance  of  twenty-five  or  thirty  paces,  and 
ascending  thirty-two  steps.  When  he  reached  the  surgeon's  room  he 
said,  "  Come  down  directly ;  I  have  taken  half  an  ounce  of  prussic 
acid."  He  then  ran  all  the  way  back  to  the  dispensary,  where  he 
was  found  standing  unsupported  in  the  middle  of  the  room.  He 
moved  his  hand  impatiently,  and  said,  "Be  quick;  give  me  some- 
thing." Some  solution  of  ammonia  was  given  him,  followed  by 
some  tincture  of  the  sesquichloride  of  iron.     He  drank  both  these, 


170  HYDROCYANIC    ACID. 

and  then,  being  directed,  put  his  finger  in  his  throat  to  induce  vomit- 
ing. This  caused  one  or  two  slight  but  abortive  efforts,  after  ^yhich 
he  suddenly  fell  flat  on  his  back,  completely  insensible.  His  face, 
previously  jmllid,  now  became  much  congested  ;  the  eyes  were  fixed 
and  half  closed  ;  the  pupils  were  somewhat  dilated ;  no  pulse  could 
be  felt ;  the  breathing  became  slow,  faint,  and  gasping ;  a  frothy 
mucus  exuded  from  between  the  lips ;  one  or  two  of  the  respirations 
were  accompanied  by  a  slight  stertorous  sound.  Xo  convulsions 
occurred.  Death  took  place  in  about  ten  minutes  after  he  first  ap- 
peared at  the  house-surgeon's  room. 

When  the  dose  is  not  sufficiently  large  to  produce  rapid  insensi- 
bility, the  first  symptoms  usually  experienced  are  giddiness  and  a 
sense  of  great  weakness ;  these  effects  are  soon  succeeded  by  irritation 
in  the  throat,  an  increased  flow  of  saliva,  nausea,  difficult  and  spas- 
modic respiration,  and  loss  of  voluntary  motion ;  the  pulse  becomes 
small  or  imperceptible,  the  face  livid,  and  the  eyes  glaring,  the  pupils 
generally  being  dilated.  These  cases  are  frequently  attended  with 
tetanic  convulsions. 

The  following  case  of  recovery  is  quoted  in  detail  by  Dr.  Stille. 
{Mat.  Med.,  ii.  210.)  A  French  physician  swallowed  a  dessert- 
spoonful of  the  medicinal  acid,  prepared  by  a  chemist  of  Paris.  He 
almost  immediately  afterward  fell  down  as  if  struck  by  lightning. 
Among  the  symptoms  observed  were  loss  of  consciousness  and 
sensibility  ;  trismus ;  a  constantly  increasing  dyspnoea ;  cold  extrem- 
ities; a  noisy  and  rattling  respiration;  the  characteristic  odor  of  the 
acid  upon  the  breath  ;  distortion  of  the  mouth  ;  and  a  thready  pulse. 
The  face  was  swollen  and  dusky,  and  the  pupils  fixed  and  dilated. 
The  trismus  increased,  and  was  soon  accompanied  by  opisthotonos. 
At  the  end  of  an  hour  a  violent  convulsion  occurred,  the  whole 
trunk  grew  stiff,  and  the  arms  were  twisted  outwards.  After  two 
hours  passed  in  this  condition,  the  patient  began  to  regain  his 
consciousness,  and  in  several  hours  afterward  he  was  able  to 
walk  without  assistance ;  but  it  was  a  fortnight  before  he  entirely 
recovered. 

In  a  non-fatal  case  reported  by  Mr,  W.  H.  Burnam,  in  which  a 
dose  containing  2.4  grains  of  the  anhydrous  acid  was  taken  by  mis- 
take, insensibility  did  not  occur  until  two  minutes  after  the  poison 
had  been  swallowed.  In  the  mean  time,  however,  the  patient,  having 
almost  immediately  discovered  his  mistake,  took  as  an  antidote  half 


PHYSIOLOGICAL    EFFECTH.  171 

an  ounce  of  aromatic  spirits  oi"  ammonia,  with  a  little  water;  and 
he  told  what  had  occurred  :  lie  spoke  hurriedly,  and  breathed  deeply. 
A  solution  of  sulphate  of  iron  was  then  administered.  The  respira- 
tion became  deeper  and  slower.  In  four  minutes  after  the  poison 
was  taken,  the  cold  douche  was  freely  employed,  and  an  additional 
quantity  of  the  iron  solution  with  spirits  of  ammonia  administered. 
Yomitino:  took  place;  and  there  was  a  slight  convulsive  shudder. 
In  twenty  minutes  the  patient  began  to  exhibit  signs  of  returning 
consciousness;  and  in  about  fifteen  minutes  later  he  was  able  to 
walk  up-stairs  to  bed.  {Brit,  and  For.  Med.-Chir.  Rev.,  April, 
1854.)  In  a  case  of  recovery  reported  by  Mr.  Garson,  in  which  a 
teaspoonful  of  the  acid,  of  unknown  strength,  had  been  taken,  the 
symptoms  were  delayed  for  about  fifteen  minutes.  The  individual 
was  then  found  in  a  state  of  insensibility,  and  this  continued  for 
about  four  houi-s,  although  active  remedies  were  employed.  This  is 
the  most  protracted  case,  in  regard  to  the  appearance  of  the  symp- 
toms, yet  recorded. 

Several  instances  are  reported  in  which  the  inhalation  of  the 
diluted  vajior  of  hydrocyanic  acid  caused  most  alarming  symptoms ; 
and  Dr.  Christisou  quotes  a  case  in  which  the  liquid  acid  applied 
to  a  wound  in  the  hand  caused  death  in  an  hour  afterward.  In  a 
case  related  by  Dr.  J.  A.  Post  {New  York  Med.  Jour.,  April,  1876), 
the  inhalation  of  the  vapor  evolved  from  cyanide  of  potassium  used 
by  a  jeweller  with  gold  as  an  alloy  caused  his  death,  under  symptoms 
of  congestion  of  the  brain,  in  about  half  an  hour  after  he  was  first 
seen  by  the  physician. 

Hydrocyanic  acid  is  also  equally  poisonous,  with  the  production 
of  similar  symptoms,  when  taken  into  the  system  in  the  form  of  an 
alkaline  cyanide.  Since  the  introduction  of  cyanide  of  potassium 
into  the  arts  for  photographic  and  other  purposes,  numerous  in- 
stances of  poisoning  by  it  have  occurred.  In  a  case  of  poisoning 
by  this  salt  related  by  Dr.  Schauenstein,  of  Vienna,  occurring  in  a 
young  man,  death  took  place  almost  instantly,  without  any  striking 
symptoms.  In  another  case,  reported  by  the  same  writer,  strong 
tetanic  spasms  came  on  directly  after  the  poison  had  been  taken, 
and  death  ensued  in  less  than  an  hour.  {Amer.  Jour.  Med.  Sei., 
Jan.  1860,  279.)  In  a  case  in  which  we  were  consulted  in  1864, 
a  man  took,  with  suicidal  intent,  about  sixteen  grains  of  the  salt 
in  solution;    immediately  after  swallowing  the  poison  he   walked 


172  HYDEOCYAISriC   ACID. 

about  six  steps,  then  fell  insensible,  and  death  ensued  in  about  five 
minutes. 

The  following  case  of  recovery  after  a  quantity  of  this  salt  had 
been  taken  is  reported  by  Dr.  Mueller- Warnek.  {London  Med. 
Record,  May,  1878.)  A  man  was  heard  to  fall  in  his  room,  and 
quickly  after  was  found  lying  on  the  floor  in  an  unconscious  state, 
holding  in  one  hand  a  letter,  and  in  the  other  a  bottle  containing  a 
solution  of  cyanide  of  potassium.  About  an  hour  later,  vomiting 
having  occurred,  the  man  was  in  a  state  of  profound  coma.  The 
skin  was  cold  and  clammy  ;  the  extremities  cold ;  face  greatly  cya- 
nosed  ;  eyeballs  projecting,  and  directed  upwards  ;  pupils  much 
dilated,  and  insensible  to  light ;  the  lower  jaw  fixed  ;  frothy  saliva, 
tinged  with  blood,  issued  from  the  mouth,  and  at  each  expiration 
there  was  a  strong  odor  of  hydrocyanic  acid.  The  muscles  of  the 
extremities  were  relaxed,  and  there  was  entire  loss  of  sensibility. 
Under  the  free  use  of  the  stomach-pump,  and  artificial  respiration 
and  stimulants,  the  patient  slowly  recovered,  but  it  was  several  days 
before  he  was  able  to  leave  his  bed. 

A  remarkable  series  of  cases  of  poisoning  by  cyanide  of  potas- 
sium is  reported  by  Dr.  A.  B.  Arnold,  of  Baltimore  [Amer.  Jour. 
Med.  Sci.,  Jan.  1869,  103),  in  which  a  solution  of  potassium  chlorate 
had  been  prescribed  for  a  child.  In  filling  the  prescription,  the 
druggist  used  the  last  portions  of  potassium  chlorate  in  the  bottle 
from  which  he  dispensed  it.  A  teaspoonful  being  given  to  the  child, 
it  was  almost  instantly  seized  with  convulsions,  and  quickly  died. 
Dr.  Arnold  then  tasted  small  portions  of  the  solution,  and  he  soon 
experienced  violent  symptoms,  and  narrowly  escaped  with  his  life. 
Finally,  the  druggist,  to  show,  as  he  said,  that  he  had  made  no  mis- 
take, took  a  portion  of  the  prescription,  and  in  a  few  minutes  after- 
ward fell  down  dead.  It  was  subsequently  learned  that  the  bottle 
from  which  the  chlorate  had  been  dispensed  had  previously  contained 
cyanide  of  potassium. 

Period  when  Fatal. — The  fatal  period  in  poisoning  by  hydro- 
cyanic acid  is  subject  to  considerable  variation ;  yet  it  is  extremely 
limited  when  compared  with  that  of  the  action  of  most  other  poisons. 
Several  instances  are  recorded  in  which  death  took  place  in  from  five 
to  ten  minutes,  and  it  has  occurred  in  two  minutes,  and  perhaps 
even  within  a  shorter  period.  On  the  other  hand,  death  has  been 
delayed  for  nearly  an  hour,  even  when  the  quantity  of  poison  taken 


PHYSIOLOGICAL   EFFECTS.  173 

was  siiffioicntly  great  to  produce  almost  immediate  insensibility. 
In  fatal  cases,  however,  life  is  rarely  prolonged  beyond  half  an 
hour:  those  who  survive  this  j)eriod  usually  entirely  recover,  in 
an  accident  that  occurred  in  one  of  the  hospitals  of  Paris,  by  which 
seven  epileptic  j)atients  were  fatally  jjoisoned  by  ccpial  quantities  of 
hydrocyanic  acid,  the  fatal  period  varied  from  fifteen  to  forty-five 
minutes. 

Dr.  Fao-o-e  relates  the  case  of  a  medical  student  who  took  about 
a  drachm  and  a  half  of  Scheele's  acid,  and  was  thereby  immediately 
rendered  insensible;  but  he  did  not  die  from  its  effects  until  from 
one  hour  and  a  quarter  to  one  hour  and  a  half  after  it  had  been 
taken.  {Guys  Hosj).  Rep.,  18G8,  259.)  This  is  the  most  protracted 
case  in  this  respect  yet  reported. 

Fatal  Qaantitij.— That  similar  quantities  of  prussic  acid  do  not 
always  produce  the  same  result  is  well  illustrated  in  the  instance  of 
the  Parisian  epileptics  just  mentioned.  The  quantity  of  the  poison 
taken  by  each  of  these  patients  is  stated  by  most  toxicological 
writers,  on  the  authority  of  Orfila,  to  have  been  equivalent  to  about 
two-thirds  of  a  grain  of  the  anhydrous  acid ;  but  it  appears  from 
more  recent  statements  (Braithivaite's  Retrospect,  xii.  125)  that  the 
quantity  actually  taken  by  each  was  equivalent  to  five  grains  and 
a  half  of  the  real  acid.  An  instance  in  which  about  two  grains  of 
the  acid  caused  death  has  already  been  cited.  In  a  case  reported  by 
Mr.  Hicks,  a  solution  containing  nine-tenths  of  a  grain  of  the  pure 
acid  proved  fatal  to  a  healthy  woman,  aged  twenty-two  years,  in 
from  fifteen  to  twenty  minutes.  This  seems  to  be  the  smallest  fatal 
quantity  yet  recorded.  Smaller  quantities  have,  however,  in  ses^eral 
instances  produced  most  dangerous  symptoms.  Several  cases  are 
reported  in  which  doses  of  only  about  five  grains  of  cyanide  of  po- 
tassium caused  death. 

On  the  other  hand,  Mr.  Bishop  has  related  a  case  in  which  a 
man  entirely  recovered  after  having  taken  at  a  dose  forty  minims 
of  a  solution  containing  one  grain  and  a  third  of  anhydrous  prussic 
acid.  {Lancet,  London,  Sept.  1845,  315.)  In  this  case  the  patient, 
according  to  his  own  account,  remained  sensible  for  at  least  two 
minutes  after  taking  the  poison.  When  first  seen  by  Mr.  Bishop, 
about  ten  minutes  after  the  occurrence,  he  was  senseless,  the  counte- 
nance ghastly  pale,  face  swollen  and  covered  with  perspiration,  the 
respiration  slow  and  labored,  the  eyes  fixed  and  glazed,  the  pupils 


174  HYDROCYANIC   ACID. 

dilated,  and  the  whole  body  in  a  rigid  state.  The  treatment  con- 
sisted in  cold  aflfusion,  ammonia,  emetics,  and  bleeding.  So,  also, 
Dr.  Christison  has  reported  a  case  in  which  a  gentleman  recovered 
after  having  taken  a  solution  equivalent  to  between  a  grain  and  a  half 
and  two  grains  of  the  anhydrous  acid.  And  in  a  case  already  cited, 
that  reported  by  Mr.  Burnam,  recovery  followed  even  after  2.4  grains 
of  the  pure  acid  in  solution  had  been  swallowed.  In  this  case,  how- 
ever, as  well  as  in  that  reported  by  Dr.  Christison,  active  remedies 
were  almost  immediately  employed. 

Treatment. — On  account  of  the  rapid  action  of  hydrocyanic 
acid  when  taken  in  poisonous  quantity,  it  rarely  happens  that  treat- 
ment can  be  resorted  to  in  time  to  be  of  much  service.  The  reme- 
dies consist  chiefly  in  the  exhibition  of  stimulants;  but  certain 
chemical  antidotes  have  also  been  advised. 

The  exhibition  of  the  vapor  of  ammonia  has  been  highly  recom- 
mended, and  several  instances  are  reported  in  which  its  use  was 
attended  with  great  advantage.  It  has  also  been  proposed  to  admin- 
ister a  solution  of  ammonia  diluted  with  water ;  but  in  this  form, 
according  to  Orfila,  it  is  of  no  service.  Chlorine,  administered 
either  in  the  form  of  vapor  or  taken  internally,  has  also  been 
strongly  advised.  It  may  be  used  in  the  form  of  a  weak  solution 
of  hypochlorite  of  lime  or  of  the  corresponding  sodium  salt.  The 
gas  is  readily  obtained  by  acting  on  either  of  these  salts  with  diluted 
hydrochloric  or  acetic  acid.  From  experiments  on  inferior  animals, 
Orfila  was  led  to  believe  that  chlorine  was  the  most  efiicient  antidote 
yet  proposed.  It  need  hardly  be  added  that  great  caution  should 
be  exercised  in  its  administration. 

Cold  affusion,  first  recommended  by  Herbst,  has  perhaps  on  the 
whole  been  found  the  most  efficient  remedy  hitherto  employed  in 
the  human  subject.  Its  use  should  be  accompanied  by  the  exhibi- 
tion of  the  vapor  of  chlorine  or  ammonia.  In  several  instances  of 
recovery,  in  which  this  treatment  was  employed,  it  was  apparently 
the  means  of  averting  death.  Artificial  respiration  was  strongly 
insisted  on  by  the  late  Dr.  Pereira.  He  successfully  employed 
it  in  experiments  on  animals.  Stimulating  injections,  as  well  as 
blood-letting,  have  also  been  advised.  The  latter  should  be  resorted 
to  with  great  caution.  In  Dr.  Warnek's  case  of  recovery,  one 
hour  after  a  large  dose  of  cyanide  of  potassium  had  been  taken, 
the  stomach  was  repeatedly  washed  by  means  of  the  stomach-pump 


POST-MORTEM    APPEARANCES.  175 

with  tepid  water,  until  the  \vashiii<;  no  longer  had  tlie  odor  of  tlie 
poison. 

As  a  chemical  antidote,  it  has  been  suggested  by  Messrs.  Smith, 
of  Edinburgh,  to  administer  a  sohition  of  a  mixture  of  the  sulphates 
of  tlie  protoxide  and  sesquioxide  of  iron  (ferrous  and  ferric  sul- 
phates), quickly  followed  by  a  solution  of  carbonate  of  potassium. 
A  mixture  of  this  kind  produces  with  hydrocyanic  acid  Prussian 
blue,  which  is  inert,  being  insoluble.  In  experiments  on  animals, 
this  treatment  was  quite  successful.  Even  if  this  antidote  be  at 
hand,  it  should  never  be  relied  on  to  the  exclusion  of  stimulants  and 
cold  atiusion. 

As  a  physiological  antidote  in  poisoning  by  hydrocyanic  acid, 
Preyer  has  strongly  advised  the  hypodermic  injection  of  atropine. 
He  found  that  rabbits  to  Avhich  atropine  had  previously  been  ad- 
ministered exhibited  a  surprising  immunity  to  the  action  of  hydro- 
cyanic acid.  But  Prof.  Boehm  and  A.  Knie,  from  experiments 
chiefly  on  cats,  deny  the  antidotal  action  of  this  substance. 

Post-mortem  Appearances, — These  will,  of  course,  depend 
somewhat  on  the  length  of  time  the  individual  survived  after  taking 
the  poison,  and  also  the  period  that  has  elapsed  since  death.  The 
face  is  usually  pale,  but  often  livid,  the  eyes  glistening  and  staring, 
the  lips  blue,  the  jaws  firmly  closed,  and  the  extremities  soon  become 
rigid.  The  blood  throughout  the  body  is  fluid,  and  generally  of  a 
dark  or  bluish  color,  but  sometimes  cherry-red;  the  venous  system 
is  turgid ;  the  arteries  are  nearly  empty ;  the  liver,  and  in  some  in- 
stances the  lungs,  much  congested.  The  stomach,  other  than  so  far 
as  cadaveric  changes  have  taken  place,  is  generally  natural.  It  need 
hardly  be  observed  that  neither  of  these  appearances  is  peculiar  to 
death  from  hydrocyanic  acid. 

In  poisoning  by  hydrocyanic  acid,  the  blood  exhibits  no  char- 
acteristic spectrum,  but  simply  that  of  oxyheemoglobin.  (C.  A.  Mac- 
Munn,  The  Spectroscope  in  Medicine,  1880,  89.)  If,  however,  hydro- 
cyanic acid  or  an  alkaline  cyanide  be  added  directly  to  the  blood,  and 
the  mixture  gently  warmed,  it  presents  under  the  spectroscope,  as 
observed  by  Preyer,  a  single  broad  absorption  band  somewhat  simi- 
lar to  that  of  reduced  haemoglobin,  only  that  it  extends  somewhat 
nearer  to  the  violet  end  of  the  spectrum,  and  this  portion  of  it  is 
the  darkest. 

One  of  the  most  striking  characters  in  death  from  this  poison  is 


176  HYDROCYANIC   ACID. 

the  exhalation  of  the  peculiar  odor  of  the  acid.  This  is  sometimes 
emitted  from  the  corpse,  even  before  any  dissections  are  made,  and, 
at  least  in  recent  cases,  is  nearly  always  exhaled  when  the  stomach 
or  thoracic  cavity  is  opened ;  and  it  is  often  detected  in  the  blood 
throughout  the  body.  As,  however,  hydrocyanic  acid  is  very  volatile, 
and  also  readily  undergoes  decomposition,  it  may  in  a  little  time  so 
far  disappear  from  the  body  that  its  odor  can  no  longer  be  recognized. 
Moreover,  the  odor  of  the  acid  is  liable  to  be  masked  by  the  presence 
of  other  odors.  In  a  singular  case  related  by  Prof.  Casper,  however, 
in  which  a  woman  had  poisoned  herself  with  a  mixture  of  prussic 
acid  and  a  variety  of  essential  oils,  and  the  body  diffused  a  sweet  odor, 
on  opening  the  stomach  such  a  powerful  aroma  of  bitter  almonds 
came  forth  as  almost  to  stupefy  every  one  present.  In  several  reported 
instances  in  which  this  character  was  not  observed  in  the  stomach,  a 
subsequent  chemical  analysis  revealed  the  presence  of  very  notable 
quantities  of  the  poison,  in  one  case  even  so  much  as  one  grain  of 
the  anhydrous  acid.  In  Dr.  Sewell's  case,  in  which  seven  drachms 
of  the  medicinal  acid  had  been  taken,  he  failed  to  detect  the  odor  of 
the  poison  upon  applying  his  nose  to  the  mouth  of  the  deceased,  very 
soon  after  death.  And  in  the  case  related  by  Mr.  Hall,  he  failed  to 
observe  the  slightest  odor  of  the  poison,  even  in  the  most  forcible 
expirations  of  the  patient,  only  some  six  or  eight  minutes  after  about 
two  grains  of  the  acid  had  been  taken,  followed  by  death  in  less  than 
twenty  minutes. 

In  a  very  profound  but  non-fatal  case  recently  reported  by  Dr. 
G.  W.  Maser  {Med.  Record,  June,  1884,  711),  the  odor  of  the  acid 
was  observed  in  the  breath  of  the  patient  for  several  days  after  the 
poison  had  been  taken. 

In  the  case  reported  by  Hufeland,  already  mentioned,  the  body 
exhaled  the  odor  of  the  acid  on  the  day  following  death.  The  coun- 
tenance was  pale  and  composed,  the  eyes  glistening,  spine  and  neck 
stiff,  and  the  back  livid.  The  blood  was  fluid,  bluish  in  color,  and 
throughout  the  body  emitted  a  very  strong  odor  of  the  poison.  The 
vessels  of  the  brain,  as  well  as  the  liver  and  lungs,  were  gorged  with 
blood ;  the  arteries  were  empty,  the  veins  distended,  and  the  mucous 
membrane  of  the  stomach  and  intestines  reddened. 

In  the  cases  of  the  seven  Parisian  epileptics,  no  odor  of  the 
poison  was  perceived  in  any  part  of  the  body  twenty-four  hours 
after  death.     The  lips,  face,  and  head  were  bloated  and  of  a  violet 


GENERAL   CHEMICAL   NATURE.  177 

cH^Ior;  the  back  livid;  iVotliy  l)loo<]  esca|>e(l  from  the  month  and 
nostrils;  the  eyes  wen;  closed,  and  the  btnly  rij^id.  The  stomach  was 
highly  injected  ;  the  liver,  s|)k'en,  and  kidneys  much  j^orged  with 
black  bUxxl ;  the  arteries  empty,  and  the  veins  turgid.  In  Mr.  Hicks's 
case,  in  which  only  nine-tenths  of  a  grain  of  the  acid  was  taken,  the 
0(ior  of  the  poison  was  plainly  perceived  on  opening  the  chest,  and 
was  also  strongly  emitted  from  the  contents  of  the  stomach,  although 
the  examination  was  not  made  until  ninety  hours  after  death. 

In  a  case  examined  by  M.  Buchner  {Amer.  Jour.  Phann.,  1869, 
465),  the  blood  was  of  a  clear  cherry-red  color,  and  preserved  this 
tint  for  several  days.  At  the  end  of  five  days  it  was  still  perfectly 
liquid,  and  some  weeks  elapsed  before  it  gelatinized.  When  pre- 
served in  stoppered  bottles,  it  resisted  putrefaction  for  a  long  time, 
but  the  red  corpuscles  were  destroyed  in  a  few  days.  It  presented 
710  odor  of  prussic  acid,  but  when  diluted  with  water  and  distilled, 
the  first  portions  of  the  distillate  possessed  a  distinct  odor  of  the 
poison,  and  gave  positive  results  witli  the  u.-ual  tests.  By  this 
means  the  acid  was  detected  even  after  the  lapse  of  fifteen  days. 

Chemical  PeopePwTies. 

General  Chemical  Nature. — Anhydrous  hydrocyanic  acid 
(HCy)  is  a  colorless,  very  volatile,  inflammable  liquid,  .of  a  peculiar 
odor.  It  readily  mixes  in  all  proportions  with  alcohol  and  water. 
The  pure  acid  has  a  specific  gravity  of  0.706,  and  boils  at  26.6°  C. 
(80°  F.),  yielding  a  combustible  vapor. 

The  medicinal  acid  is  usually  obtained  by  distilling,  at  a  moderate 
heat,  a  solution  of  ferrocyanide  of  pota.ssium,  K^FeCyg,  with  dilute 
sulphuric  acid,  and  collecting  the  product  in  water,  contained  in  a 
cooled  receiver.  The  reaction  is  as  follows:  2K^FeCyg-|- 6H2SO^^ 
6KHSO^H-K2Fe2Cy6+6HCy.  The  commercial  acid,  when  pure, 
has  a  very  feeble  acid  reaction,  and  a  density  varying  with  its 
strength;  when  it  contains  about  three  per  cent,  of  the  acid,  its  spe- 
cific gravity  is  about  0.998. 

When  hydrocyanic  acid  is  brought  in  contact  with  a  solution  of 
an  alkaline  hydrate,  both  the  acid  and  alkaline  compound  undergo 
decomposition,  with  the  formation  of  a  salt,  or  cyanide,  of  the  metal, 
and  the  production  of  water;  thus:  KHO-f- HCy=KCy-fH20. 
These  salts  are  freely  soluble  in  water;  they  are  readily  decomposed 
by  acids,  with  the  evolution  of  free  hydrocyanic  acid.     When  ex- 

12 


178  HYDROCYANIC   ACID. 

posed  to  the  air,  either  in  their  solid  state  or  in  solution,  they  slowly 
absorb  carbonic  acid,  and  thus  become  changed  into  carbonates,  the 
eliminated  prussic  acid  being  dissipated  in  the  form  of  vapor.  The 
cyanides  of  the  metals  proper,  unlike  those  of  the  alkalies,  are  for 
the  most  part  insoluble  in  water;  but  many  of  them  are  freely 
soluble  in  a  solution  of  an  alkaline  cyanide,  with  the  formation 
of  a  double  salt. 

Special  Chemical  Properties. — It  has  been  claimed  by  sev- 
eral toxicological  writers  that  the  odor  of  hydrocyanic  acid  serves 
to  detect  the  presence  of  smaller  quantities  of  the  poison  than  can  be 
recognized  by  any  of  the  chemical  tests ;  but  this  is  an  error,  even 
in  regard  to  the  vapor  from  perfectly  pure  solutions  of  the  acid. 
Nevertheless,  under  certain  conditions,  extremely  minute  quantities 
of  the  acid  may  thus  be  recognized.  We  have  found,  in  repeated 
experiments,  that  when  ten  grains  of  a  l-50,000th  solution  of  the 
pure  acid  (=-g-^^  grain  HCy)  are  enclosed  for  some  time  in  a  small 
test-tube,  and  the  tube  then  opened,  the  peculiar  odor  of  the  poison 
is  sufficiently  marked  to  be  described  by  persons  entirely  ignorant 
of  the  true  nature  of  the  solution.  With  a  similar  quantity  of  a 
l-100,000th  solution  an  odor  is  perceptible,  but  its  peculiar  char- 
acter is  lost.  It  need  hardly  be  repeated  that  the  odor  from  even 
strong  solutions  of  the  poison  may  be  entirely  disguised  by  the  pres- 
ence of  other  odors. 

There  are  but  few  chemical  tests  to  which  we  resort  for  the  detec- 
tion of  hydrocyanic  acid,  but  these  are  so  characteristic  and  delicate 
in  their  reactions  as  to  leave  nothing  more  to  be  desired  in  this 
respect.  Moreover,  they  are  equally  applicable  for  the  detection  of 
the  vapor  of  the  poison.  In  the  following  examination  of  these 
tests,  the  fractions  employed  indicate  the  quantity  of  anhydrous  prus- 
sic acid  in  solution  in  one  grain  of  pure  water.  The  results,  unless 
otherwise  stated,  refer  to  the  behavior  of  one  grain  of  the  solution. 

1.  Silver  Nitrate. 

Nitrate  of  silver  throws  down  from  solutions  of  free  hydrocyanic 
acid,  and  of  soluble  cyanides,  a  white  amorphous  precipitate  of  cy- 
anide of  silver,  AgCy,  which  is  insoluble  in  the  fixed  caustic  alka- 
lies, and  only  sparingly  soluble  in  ammonia,  but  readily  soluble  in 
the  alkaline  cyanides.  Cold  nitric  acid  fails  to  dissolve  it,  but  it  is 
soluble  in  the  hot  concentrated  acid ;  hydrochloric  acid  decomposes 


i^lIA'ER   TEST.  \7U 

it  with   the   fonuiitioii    of  chloiidc   of  silver   and    tlic   cvolutidn   oC 
hyilrocyaiiic  acid. 

1.  yItg  grain  of  Ijydroeyanic  acid,  in  one  trrain  of  water,  yields  a 

very  copious  precipitate,  which  does  not  entirely  disappear  wIkii 
the  mixture  is  heated  with  several  drojis  of  strong  iiitri<;  acid. 

2.  yo^yo  grain  yields  a  (copious   precipitate,  which    readily  dissolves 

on  the  addition  of  a  drop  of  strong  ammonia;  but  dissolves 
with  difficulty,  in  the  mixture,  in  several  droj)s  of  warm  nitric 
acid. 

3.  TTf.VoT  g'*^i"  '•  '1  quite  good  flocculent  precipitate. 

4.  ^s^.VuTF  grain  yields  no  immediate  precipitate,  but  in  a  very  little 

time  the  mixture  becomes  turbid,  and  soon  there  is  a  very 
satisfactory  deposit. 

5.  ^ly.oinr  grain  :  after  a  little  time  a  very  distinct  opalescence,  and 

soon  a  very  perceptible  deposit. 
^'  TinF.lFinF  grain  :  in  a  few  minutes  the  mixture  becomes  very  dis- 
tinctly turbid. 

Fallacies. — Nitrate  of  silver  also  produces  white  precipitates  in 
solutions  of  free  hydrochloric  acid,  of  chlorides,  carbonates,  phos- 
phates, tartrates,  and  some  other  salts,  and  also  with  various  kinds 
of  organic  matter.  These  precipitates,  however,  except  that  from 
chlorine,  are  readily  soluble  in  strong  nitric  acid,  in  which  they  differ 
from  the  cyanide  compound.  The  chloride  of  silver  readily  darkens 
when  exposed  to  light,  whereas  the  cyanide  remains  unchanged  in 
color ;  again,  the  former  salt  is  readily  soluble  in  ammonia,  whilst 
the  latter  is  not,  unless  present  only  in  very  minute  quantity.  Tol- 
erably strong  solutions  of  iodides  and  bromides,  and  of  their  free 
acids,  yield  with  nitrate  of  silver  yellowish-white  precipitates;  from 
dilute  solutions,  however,  these  precipitates,  in  regard  to  color,  might 
readily  be  mistaken  for  the  cyanide  compound,  especially  when  they 
are  obtained  from  organic  mixtures :  like  the  cyanide  deposit,  they 
are  nearly  insoluble,  or  dissolve  with  difficulty,  in  cold  nitric  acid. 

The  cyanide  of  silver  is  readily  distinguished  from  all  other  pre- 
cipitates produced  by  this  reagent,  in  that  when  thoroughly  dried 
and  heated  in  a  narrow  reduction-tube  it  undergoes  decomposition 
with  the  evolution  of  cyanogen  gas,  which,  when  ignited,  burns  with 
a  rose-colored  flame.  If  this  decomposition  be  effected  in  a  small 
tube,  which  after  the  introduction  of  the  dried  cyanide  has  been 
drawn  out  into  a  very  narrow  capillary  neck,  beginning  something 


180  HYDROCYANIC   ACID. 

less  than  an  inch  above  the  cyanide  compound,  the  1-lOOth  of  a 
grain  of  the  salt  will  yield  satisfactory  results.  For  the  success  of 
this  experiment  it  is  essential  that  the  cyanide  be  thoroughly  dried 
before  being  introduced  into  the  tube. 

Vapor  of  Hydrocyanic  Acid. — When  the  vapor  of  prussic  acid 
is  received  on  a  drop  of  nitrate  of  silver  solution,  the  latter  becomes 
coated  with  a  white  film  of  cyanide  of  silver,  which,  especially  from 
dilute  solutions  of  the  acid,  is  crystalline,  and  most  abundant  along 
the  margin  of  the  drop.  In  its  behavior  with  reagents  this  deposit 
has  the  properties  already  described.  This  test  may  be  applied  by 
placing  a  drop  of  the  acid  solution  in  a  watch-glass,  and  covering 
the  latter  with  a  similar  inverted  glass,  containing  a  small  drop  of 
the  silver  solution.  By  this  method  one  grain  of  the  acid  solution 
yields  as  follows : 

1.  y^  grain  of  hydrocyanic  acid,  in  one  grain  of  water:  an  imme- 

diate cloudiness  is  observed  in  the  silver  solution,  and  in  a  very 
little  time  there  is  a  quite  copious  white  deposit.  Under  the 
microscope,  the  deposit  has  the  appearance  of  an  amorphous 
mass,  but  if  broken  up  with  the  point  of  a  needle  it  will  be 
found  to  consist  of  very  small  but  distinct  crystals.  If  the 
watch-glass  containing  the  poison  be  first  placed  on  the  stage  of 
the  microscope  and  then  covered  by  the  glass  containing  the 
silver  solution,  the  formation  of  the  crystals  may,  at  least  for  a 
time,  be  observed. 

2.  YFTo  gi'ai"  '•  8^11  immediate  cloudiness  appears  in  the  reagent  solu- 

tion, and  soon  there  is  a  quite  good,  white  film.  If  its  formation 
be  observed  under  the  microscope,  the  crystals  will  be  found  to 
form  more  slowly  and  become  somewhat  larger  than  in  1. 

3.  Yo.Voo"  g'^^i'i  •  ii^  ^  little  time  a  cloudiness  appears,  and  after  a  few 

minutes  there  is  a  quite  good  deposit,  which  consists  principally 
of  irregular  crystals,  varying  from  the  1-lOOOth  to  the  l-2000th 
of  an  inch  in  length,  of  the  forms  illustrated  in  Plate  IV.,  fig.  1. 
Usually,  small  granules,  prisms,  and  needles  form  along  the 
margin  of  the  drop. 

4.  2T,Wo  graio  :  after  a  little  time  the  margin  of  the  silver  solution 

becomes  white,  and  soon  there  is  a  good  crystalline  deposit. 

5.  -g-o.Wo   gr^iii  '•  when  a  very  small  drop  of  the  reagent  solution  is 

employed,  crystals  appear  in  less  than  two  minutes,  and  before 
long  there  is  a  very  satisfactory  deposit. 


IltON    TRST.  IHI 

6.  ^^  ^^^^  grain  :  after  a  few  inimitos  crvHtals  can  be  seen  with  the 
microscope,  and   after  .some   minutes   they  are  qnite  evident   to 
the  nuked  eye.     The  deposit  is  confined   to   the   niai-^in  of  the 
drop,  and  chiefly  consists  of  grannies,  small  prisms,  and  needles, 
Plate  IV.,  fig.  2.     So  far  as  the  evidence  of  the  presence  of 
hydrocyanic  acid  is  concerned,  this  qnantity  furnishes  as  un- 
equivocal results  as  any  larger  amount.     The  formation  of  the 
deposit  is  much  facilitated  by  applying  the  warmth  of  the  hand 
to  the  watch-glass  containing  the  acid  solution. 
It  need  lianlK-  be  observed  that  if  the  silver  solution  becomes 
nearly  dry  from  evaporation,  ciystals  of  nitrate  of  silver  may  sepa- 
rate; but  these  have  a  very  different  form  from  those  of  the  cyanide, 
and,  moreover,  they  immediately  disappear  on  the  addition  of  a  very 
small  drop  of  water,  whilst  the  cyanide  crystals  are  almost  wholly 
insoluble  in  this  liquid. 

The  vapors  of  chlorine,  bromine,  and  iodine,  and  of  their  hydro- 
gen acids,  also  yield  white  or  nearly  white  films  with  a  solution  of 
nitrate  of  silver.  The  deposits  from  all  these  substances,  however, 
are  amorphous;  whereas  the  cyanide  compound  is  always  crystalline, 
even  when  obtained  from  complex  organic  mixtures  of  the  acid,  pro- 
vided sulphuretted  hydrogen,  or  some  other  gaseous  substance  which 
also  produces  a  deposit  with  the  reagent,  is  not  present.  The  odor 
of  these  substances,  as  well  as  that  of  hydrocyanic  acid,  would  gen- 
erally suffice  to  determine  the  true  nature  of  the  film  produced  by 
these  various  vapors,  even  without  the  aid  of  the  microscope.  The 
deposits  produced  by  the  vapors  of  bromine  and  iodine  have  a  faint 
yellowish-white  color.  It  may  be  remarked  that  the  vapors  of  chlo- 
rine and  of  hydrochloric  acid  generally  cause  the  dispersion  of  the 
silver  solution,  so  that  it  trickles  down  the  inside  of  the  inverted 
watch-glass;  and  the  films  produced  by  them  are  quite  thin,  even 
wljen  occasioned  by  the  pure  gases. 

2.  Iron  Test. 

"When  a  solution  of  free  hydrocyanic  acid  is  treated  with  a  solution 
of  potassium  or  sodium  hydrate,  and  then  with  a  solution  of  ferrous 
sulphate  which  has  been  exposed  to  the  air  and  contains  some  feriic 
sulphate,  it  yields  a  precipitate  of  Prussian  blue,  Fe^SFeCyg,  mixed 
with  more  or  less  monoxide  and  sesquioxide  of  iron :  this  mixture 
may  have  either  a  yellowish-brown,  greenish,  or  bluish  color,  the  hue 


182  HYDROCYANIC    ACID. 

depending  upon  the  relative  quantities  of  the  iron  compounds  present. 
On  treating  this  mixture  with  a  few  drops  of  hydrochloric  or  sul- 
phuric acid,  the  oxides  of  iron  dissolve,  while  the  Prussian  blue  re- 
mains in  the  form  of  a  deep  blue  deposit,  it  being  insoluble  in  the 
acid.  Should  the  hydrocyanic  acid  already  exist  in  the  form  of  an 
alkaline  cyanide,  the  addition  of  the  potassium  or  sodium  solution 
should  be  omitted.  In  a  solution  of  free  prussic  acid,  the  iron  com- 
pounds alone  produce  no  change. 

The  object  of  the  addition  of  the  free  alkali  in  the  above  process 
is  to  convert  the  free  hydrocyanic  acid  into  an  alkaline  cyanide. 
When  this  salt  is  then  treated  with  the  ferrous  and  ferric  sulphates, 
a  double  decomposition  takes  place,  in  which  the  alkaline  cyanide 
becomes  changed  into  potassium  sulphate,  and  the  iron  sulphates  into 
cyanides  of  iron;  thus:  18KCy  +  3FeS04+2Fe23SO^=9K2S04  + 
3FeCy2  +  2Fe2Cy6 ;  the  elements  of  the  iron  cyanides  then  coalesce 
to  form  Prussian  blue  (SFeCyg  +  2Fe2Cy6=Fe43FeCy6).  It  is  thus 
obvious  that  the  presence  of  both  the  iron  salts  is  necessary  for  the 
production  of  the  blue  compound.  The  oxides  of  iron  precipitated 
by  any  excess  of  the  alkali  employed  are  dissolved  by  the  hydro- 
chloric or  sulphuric  acid  added,  as  chlorides  or  sulphates  of  iron. 

In  very  dilute  solutions  of  hydrocyanic  acid,  the  test  fails  to  pro- 
duce an  immediate  precipitate ;  but  the  liquid,  after  the  addition  of 
the  mineral  acid,  immediately  acquires  a  greenish  color,  and  after  a 
time  deposits  flakes  of  the  blue  compound.  Such  solutions  also  re- 
quire a  proper  adjustment  of  the  alkali  and  iron  solutions.  A  large 
excess  of  the  alkali  will  decompose  the  Prussian  blue,  while  a  similar 
excess  of  the  iron  mixture  produces  with  hydrochloric  acid  a  yellow 
liquid  which  may  hold  in  solution  a  small  quantity  of  the  blue  com- 
pound. When,  therefore,  the  addition  of  hydrochloric  acid  produces 
a  yellow  solution  from  which  no  Prussian  blue  separates,  even  after 
a  time,  the  experiment  should  be  repeated  with  a  less  quantity  of  the 
iron  solution  before  pronouncing  hydrocyanic  acid  entirely  absent. 
There  is  no  difficulty  in  the  application  of  the  test,  except  in  very 
dilute  solutions  of  the  poison.  In  no  case  should  any  inference  be 
drawn  from  the  color  of  the  precipitate  prior  to  the  addition  of  the 
mineral  acid,  since  it  may  have  a  bluish  color  even  in  the  absence  of 
prussic  acid. 

When  one  grain  of  a  solution  of  hydrocyanic  acid  is  treated  as 
above,  it  yields  the  following  results : 


IRON    TRST.  183 

1.  y^  «]jr:\iii  of  tlx"  |)in-o  ju-id  yic^lds  :i  very  copious  deposit  of  Prus- 

sian 1)1  IK'. 

2.  jTjVir  J?''=i'"  '■  '^  ^'*''y  ^ood  deposit. 

3.  t^jVc"  S^^'"  •  ^  i^reeiiisli-hluo,  flocculent  j)r('cipitate  and  a  greenish 

solution  ;  after  a  time,  the  deposit  increases  in  quantity  and  ac- 
quires a  deeper  blue  color,  Sohitions  dilute  as  this,  especially 
when  only  a  single  drop  is  operated  upon,  require  a  proper  ad- 
justment of  the  reagent  solutions:  when  these  are  very  strong, 
only  a  very  small  drop  of  each  should  be  employed. 

4.  x^.VuTJ"  grai"  :  with  a  very  small  quantity  of  the  reagent  solutions, 

yields  a  quite  perceptible  greenish-blue,  flocculent  precipitate, 
with  a  greenish  solution  ;  after  the  mixture  has  stood  some  little 
time,  the  result  is  perfectly  satisfactory. 

5.  yj.VuT  g''f^in  yields  just  perceptible  greenish  flakes,  and,  after  a 

few  hours,  a  quite  distinct  deposit,  which,  when  examined  by  a 
hand-lens,  has  a  well-marked  blue  color. 

The  production  of  a  blue  precipitate  insoluble  in  hydrochloric 
acid  by  this  test  is  perfectly  characteristic  of  hydrocyanic  acid,  or  at 
least  of  a  cyanide.  At  the  same  time,  the  reaction  is  not  interfered 
with  bv  anv  substance  at  all  likelv  to  be  met  with  in  medico-lesfal 
investigations. 

Vapor  of  Hydrocyanic  Acid. — In  the  application  of  this  test  for 
the  detection  of  the  vapor  of  the  poison,  the  vaj)or  is  received  for 
some  minutes  on  a  drop  of  potassium  hydrate  solution,  by  which 
it  will  be  absorbed  as  potassium  cyanide,  without,  however,  any 
visible  change ;  the  solution  is  then  treated  with  the  iron  mix- 
ture and  hydrochloric  acid,  in  the  manner  above  described.  The 
vapor  from  one  grain  of  a  l-5000th  solution  of  the  poison  will, 
when  the  manipulations  are  conducted  with  great  care,  yield  quite 
satisfactory  results.  This,  however,  is  about  the  limit  of  the  vapor 
reaction. 

This  method  may  be  employed  to  confirm  the  nature  of  the 
cyanide  of  silver  produced  by  the  preceding  reagent.  For  this  pur- 
pose the  washed  deposit,  placed  in  a  watch-glass,  is  treated  with  a 
drop  of  hydrochloric  acid,  and  the  vapor  of  the  hydrocyanic  acid 
thus  eliminated  absorbed  by  a  drop  of  potassium  hydrate  solution, 
in  the  manner  just  pointed  out.  By  this  process  the  true  nature  of 
a  much  less  quantity  of  the  silver  precipitate  may  be  fully  established 
than  by  the  method  of  reduction,  heretofore  described. 


184  HYDROCYANIC    ACID. 

3.  Sulphur  Test. 

When  a  solution  of  free  hydrocyanic  acid  or  of  an  alkaline 
cyanide  is  treated  with  a  solution  of  yellow  sulphide  of  ammo- 
nium, and  the  mixture  gently  heated,  it  gives  rise  to  sulphocya- 
nide  of  ammonium,  NH^CyS,  which,  when  treated  with  a  ferric 
salt,  yields  a  deep  blood-red  solution  of  sulphocyanide  of  iron, 
FcgGCyS.  This  reaction  was  first  pointed  out  in  1847,  by  Prof. 
Liebig. 

In  applying  this  test,  a  few  drops  of  the  prussic  acid  solution, 
placed  in  a  small  white  dish  or  watch-glass,  are  treated  with  a  drop 
of  the  ammonium  sulphide,  and  the  mixture  evaporated  at  a  moderate 
temperature  on  a  water-bath  to  near  dryness.  Should  the  residue 
have  a  yellow  color,  it  is  moistened  with  a  drop  of  water  and  again 
evaporated.  The  cooled  residue — consisting  of  ammonium  sulpho- 
cyanide, often  in  its  crystalline  state,  and  a  white  film  of  sulphur — 
is  then  treated  with  a  drop  of  a  colorless  solution  of  ferric  sulphate 
or  of  ferric  chloride,  when  the  mixture  will  immediately  assume, 
unless  very  dilute,  a  very  deep  blood-red  color.  If  the  excess  of 
ammonium  sulphide  added  has  not  been  entirely  decomposed  or  vola- 
tilized, the  iron  reagent  will  produce  a  black  precipitate  of  sulphide 
of  iron  ;  this,  however,  is  readily  dissolved  by  a  drop  of  dilute  hydro- 
chloric acid,  without  interfering  with  the  red  color  of  the  mixture, 
unless  it  is  very  feeble. 

1.  YTo  gi'^iii  of  hydrocyanic  acid,  when  treated  as  above,  yields  a 

beautiful  blood-red  solution. 

2.  YFTo  gi'sii^  yields  an  orange-colored  mixture. 

3.  37o',Wo  g^'^'in  '    the   final    solution  has  a  very  satisfactory  light 

orange  hue. 

4.  2T.V0T  g^^i^^   yields  a  mixture  having  a  distinct  reddish  tint. 

The  color  of  this  mixture  is  quite  well  marked  when  compared 
with  that  of  the  reagents  alone. 

5.  s-o.VoT  gi'3'ij^  yields  a  just  perceptible  coloration. 

The  red  color  produced  by  this  test  is  immediately  discharged 
by  corrosive  sublimate,  and  by  nitric  acid ;  but  it  is  unaffected  by 
even  very  large  excess  of  strong  hydrochloric  acid,  except  from  very 
dilute  solutions,  when  it  is  readily  destroyed  by  an  excess  of  this 
acid.  It  is  also  discharged,  to  a  faint  reddish  hue,  by  an  alkaline 
acetate,    but    immediately   restored    upon    the    addition    of    hydro- 


SULPHUR    TEST.  185 

chloric  acid;  ammonia  causes  it  to  disappear,  with  llic  precipitiitioii 
of  sesquioxide  of  iron. 

Fallacies. — Ferric  salts  also  strike  a  deep  l)lo()(l-red  color  with 
solutions  of  iiieconic  acid.  This  color,  however,  is  not  discharged 
by  corrosive  sublimate,  nor  is  it  affected  by  an  alkaline  acetah;,  and 
it  is  readily  changed  to  yellow  or  reddish-yellow  hy  an  excess  of 
hydrochloric  acid.  The  reagent  also  changes  very  drong  solutions  of 
the  alkaline  acetates  to  a  deep  dark-red  color,  due  to  the  formation 
of  ferric  acetate:  this  color,  however,  is  immediately  discharged  to  a 
faint  yellow  tint  by  even  a  very  small  quantity  of  hydrochloric  acid. 
In  this  connection  it  may  be  remarked  that  both  meconic  acid  and 
the  alkaline  acetates  are  destitute  of  odor. 

The  objections  just  mentioned  are  the  only  ones  that  can  reason- 
ably be  urged  against  the  sulphur  test,  and  they  are  readily  answered. 
When,  therefore,  a  susjiected  solution  yields  with  the  test  a  strong 
red  color,  unaffected  by  large  excess  of  hydrochloric  acid,  there  is 
no  doubt  of  the  presence  of  a  sulphocyanide ;  yet,  should  the  color 
be  only  faint,  its  disappearance  on  the  addition  of  the  acid  would 
not  prove  the  entire  absence  of  the  poison. 

Vapor  of  Hydrocyanic  Acid. — The  sulphur  test  may  also  be  ap- 
plied for  the  detection  of  the  vapor  of  the  acid,  as  iirst  suggested  by 
Dr.  A.  Taylor.  For  this  purpose,  a  drop  of  the  ammonium  sulphide 
solution,  contained  in  an  inverted  watch-glass,  is  exposed  to  the 
evolved  vapor  for  some  minutes,  and  then  examined  in  the  manner 
above  described. 

The  vapor  evolved  from  the  1-1 0,000th  of  a  grain  of  prussic 
acid,  in  one  grain  of  water,  will  after  this  method,  providing  the 
ammonium  solution  has  been  exposed  to  the  vapor  from  ten  to  fifteen 
minutes,  yield  a  very  distinct  coloration;  but  the  result  could  hardly 
be  claimed  to  be  satisfactory.  It  need  hardly  be  added  that  when 
the  sulphur  test  is  applied  in  this  manner  it  is  free  from  the  fallacies 
that  hold  in  its  direct  application  to  a  suspected  liquid. 

The  sulphur  test  may  also  be  employed  to  confirm  the  precipi- 
tate ])roduced  by  the  silver  reagent.  For  this  purpose,  the  washed 
precipitate  is  treated  with  a  few  drops  of  sulphide  of  ammonium, 
and  the  mixture  evaporated,  at  a  gentle  temperature,  to  dryness. 
In  this  operation,  the  cyanide  of  silver  will  be  decomposed  by  the 
ammonium  compound,  with  the  formation  of  silver  sulphide  and 
ammonium  sulphocyanide.     On  now  treating  the  dry  residue  with  a 


186  HYDROCYANIC   ACID. 

little  water,  the  ammonium  salt  will  dissolve,  and  the  solution,  after 
filtration  and  concentration,  will  yield  the  usual  blood-red  color 
when  treated  with  a  persalt  of  iron. 

So,  also,  this  test  may  be  applied  to  the  vapor  evolved,  when 
the  cyanide  of  silver  is  decomposed  by  a  drop  of  strong  hydro- 
chloric acid. 

Relative  Delicacy  of  the  foregoing  Tests. — In  regard 
to  the  relative  value,  in  this  respect,  of  the  Silver  and  Iron  tests,  it 
may  be  observed  that  when  they  are  applied  to  the  vapor  of  the 
poison  the  former  is  much  the  more  delicate,  while  for  solutions  the 
latter  is  much  the  more  susceptible.  It  is  true  that  the  silver  test 
will  produce  a  precipitate  with  a  much  less  quantity  of  the  poison 
than  the  iron  test  will  reveal ;  yet  the  silver  deposit  cannot  in  itself 
be  regarded  as  peculiar  until  it  yields  an  inflammable  gas  when 
heated  in  a  reduction-tube,  for  which  purpose  it  requires,  with  the 
greatest  care,  the  precipitate  corresponding  to  at  least  the  l-500th  of 
a  grain  of  the  poison,  and  even  the  deposit  from  this  single  quantity 
could  by  no  means  be  collected  and  confirmed :  but  the  iron  test 
produces  a  characteristic  reaction  with  one  grain  of  a  1-1 0,000th 
solution  of  the  poison. 

On  the  other  hand,  when  applied  to  the  vapor  of  hydrocyanic 
acid,  the  iron  reaction  has  its  limit  with  about  the  1— 5000th  of  a 
grain  of  the  acid,  whilst  the  silver  test  yields  a  satisfactory  result 
with  the  l-100,000th  of  a  grain,  in  one  grain  of  water.  In  other 
words,  for  solutions  the  iron  test  is  about  twenty  times  more  delicate 
than  the  silver  test,  while  for  the  vapor  of  the  poison  the  silver 
reaction  is  about  twenty  times  more  delicate  than  the  iron  test. 

In  regard  to  the  Sulphur  test,  when  applied  to  solutions  of  the 
acid,  it  is  somewhat  more  delicate  than  the  iron  reaction,  and  so  also 
in  regard  to  the  detection  of  the  vapor,  but  in  the  latter  respect  it  is 
very  much  inferior  to  the  silver  method.  From  a  review  of  these 
tests,  it  is  obvious  that  should  a  suspected  solution  fail  to  yield  a 
precipitate  with  silver  nitrate,  it  would  be  useless  to  apply  either  of 
the  other  tests ;  yet  it  should  be  remembered  that  a  solution  which 
only  yields  a  faint  reaction  with  the  silver  reagent  may  evolve  a 
vapor  that  will  yield  with  it  very  satisfactory  results. 

The  comparative  value  of  these  tests  may  be  approximatively 
exhibited  as  follows : 


SEPARATION    FROM    OROANFC    MIXTURES.  187 

Silver  test,  witli  Snlutions,  ^^„  t^raiii  ;   with  Vupor,  xisj/.Tiffiy  i^''"'"- 
Iron  test,         "  "      jo.ooo  f^'""'"  i      "  "  Wcff  g^aiii. 

Sulplnir  test,  "  "      ^^.V^^  grain ;       "  "         rJS.hs  gi^a'"- 

It  need  hardly  be  observed  that  these  results  are  based  ii|)on  the 
assumption  that  the  poison  is  in  solution  in  one  (jr  a  in  of  pure  water, 
and,  it  may  be  added,  manipulated  with  care  by  experienced  hands. 

Other  Tests. — For  the  detection  of  hydrocyanic  acid,  Lassaigne 
advised  to  precipitate  it  by  a  solution  of  Copper  Sulphate,  as  copper 
cyanide ;  but  in  every  respect  this  test  is  inferior  to  those  already 
mentioned. 

Mercurous  Nitrate  produces  in  solutions  of  free  hydrocyanic  acid, 
and  of  alkaline  cyanides,  a  dark  gray  or  nearly  black  precipitate  of 
finely  divided  metallic  mercury.  This  reaction  serves  to  distinguish 
hydrocyanic  acid  and  its  simple  salts  from  hydrochloric  acid  and  its 
compounds,  which  yield  with  the  reagent  a  white  precipitate  of  mer- 
curous chloride,  or  calomel.  The  application  of  this  test,  for  this 
purpose,  would  of  course  be  unnecessary  if  the  iron  or  sulphur  test 
has  been  applied. 

Schonbein's  Test. — This  consists  in  moistening  a  slip  of  guaiacum- 
paper  with  a  solution  of  copper  sulphate,  and  exposing  it  to  the  action 
of  hydrocyanic  acid,  when  it  will  immediately  assume  a  deep  blue 
color.  The  guaiacum -paper  is  prepared  by  steeping  filtering-paper 
in  about  a  three  per  cent,  solution  of  guaiacum  resin,  and  drying  it. 
For  the  copper  solution,  one  part  of  the  sulphate  may  be  dissolved 
in  five  hundred  parts  of  water.  At  the  moment  of  use,  the  test- 
paper  is  moistened  with  the  copper  solution  and  then  exposed  to  the 
hydrocyanic  acid,  either  diffused  in  the  air  as  vapor  or  dissolved  in 
water.  M.  Schonbein  states  that  the  delicacy  of  this  reaction  is  such 
that  even  one  part  of  the  vapor  of  the  acid  in  120,000,000  parts  of 
air  will  yield  the  blue  coloration.  This  reaction,  however,  is  not 
peculiar  to  hydrocyanic  acid,  since  ozone,  chlorine,  and  several  other 
vapors  produce  a  similar  coloration. 

Separation  from  Organic  Mixtures. 

As  hydrocyanic  acid  is  liable  to  be  rapidly  dissipated  in  the 
foriu  of  vapor,  and  even  to  undergo  spontaneous  decomposition,  the 
examination  of  a  mixture  in  which  its  presence  is  suspected  should 
not  be  delayed.     The  same  method  of  research  will  apply  equally  to 


188  HYDROCYANIC   ACID. 

suspected  articles  of  food  or  medicine,  the  matters  vomited,  and  the 
contents  of  the  stomach.  Before  resorting  to  the  application  of  any 
chemical  test,  the  suspected  mixture  should  be  carefully  examined  in 
resrard  to  its  odor :  but  it  must  be  borne  in  mind  that  mixtures  of 
this  kind  may  contain  a  very  notable  quantity  of  the  poison  without 
emitting  its  peculiar  odor. 

Examination  for  the  Vapor. —  For  this  purpose,  the  suspected 
mixture  is  placed  in  a  glass  jar  or  any  similar  vessel,  and  the  mouth 
of  the  vessel  then  covered  by  an  inverted  watch-glass  in  which  has 
been  previously  placed  a  drop  of  nitrate  of  silver  solution.  Sooner 
or  later,  even  if  only  a  minute  trace  of  the  vapor  is  being  evolved 
from  the  mixture,  the  silver  solution  will  acquire  a  white  incrustation 
of  cyanide  of  silver.  Any  deposit  thus  produced  is  then  examined 
under  the  microscope :  at  the  same  time,  the  mouth  of  the  bottle 
should  be  closed  by  a  cork,  or  by  another  Avatch-glass  containing  a 
drop  of  the  silver  reagent.  Should  the  microscope  reveal  the  presence 
of  crystals  of  the  forms  already  described,  these  will  fully  establish 
the  presence  of  the  poison,  since  there  is  no  other  substance  that  will 
yield  similar  results.  Should,  however,  the  deposit  be  amorphous, 
it  may  still,  in  part  at  least,  be  due  to  the  cyanide;  but  it  might  be 
due  to  the  presence  of  chlorine,  or  possibly  to  the  vapor  of  bromine 
or  of  iodine.  Under  these  circumstances,  the  true  nature  of  the 
deposit,  if  cyanide  of  silver,  may  be  established  either  by  the  iron 
or  the  sulphur  test  in  the  manner  already  indicated.  One  or  both 
of  these  latter  tests  should  also  be  applied  directly  to  the  suspected 
mixture,  even  in  case  the  silver  reaction  is  satisfactory. 

Should  the  silver  solution,  after  an  exposure  of  several  minutes, 
fail  to  indicate  the  presence  of  the  poison,  the  suspected  mixture 
should  be  occasionally  agitated  by  shaking  the  bottle,  and  the  appli- 
cation of  the  reagent  be  continued  for  half  an  hour  or  longer.  If 
there  is  still  no  evidence  of  the  presence  of  the  poison,  it  is  not  likely 
that  it  would  be  detected  by  this  method,  even  if  applied  for  several 
hours  ;  yet  it  must  not  be  concluded  that  the  poison  is  entirely  absent 
even  in  its  free  state,  since  it  may  be  strongly  retained  by  organic 
substances.  In  case  the  silver  reagent  should  fail  to  receive  a  deposit, 
it  would  of  course  be  useless  to  apply  either  of  the  other  tests  for 
the  vapor. 

Method  hy  simple  Distillation. — After  testing  the  suspected  liquid 
in  regard  to  its  reaction  and  setting  apart  a  small  portion,  for  future 


SEPARATION    FROM    OIKJANIC    MIXTURES.      '  180 

exnniination  if  necossarv,  tlio  renminiiij^  portion  is  placed  in  a  retort 
liavin<j^  its  nocU  slightly  inclined  upwards  and  connected,  hy  means 
of"  a  bent  tube  and  corks,  with  a  I^iebig's  condenser,  the  lower  end 
of  which  opens  into  an  ordinary  receiver.  In  the  absence  of  Lie- 
big's  condenser,  tiie  retort  may  be  connected  dircdlv  with  a  well- 
cooled  receiver.  The  liquid  is  then  distilled  at  a  moderate  heat,  by 
means  of  a  water-bath,  until  about  one-eighth  of  the  fluid  has  passed 
over  into  the  receiver.  On  account  of  its  volatile  nature,  any  free 
hydrocyanic  acid  originally  present  in  the  liquid  will  now  be  found 
in  the  distillate,  which  may  be  examined  in  the  usual  manner. 

If  prussic  acid  is  thus  obtained  and  the  original  liquid  was  des- 
titute of  a  strongly  acid  reaction,  then  there  is  little  doubt  that  the 
poison  was  present  in  its  free  state;  yet  it  may  have  existed  as  an 
alkaline  cyanide,  but  it  could  not  have  been  in  the  form  either  of  a 
ferro-  or  sulpho-cyanide.  To  determine  whether  it  existed  iu  its  un- 
combiued  state  or  as  an  alkaline  cyanide,  a  portion  of  the  reserved 
fluid  is  treated  with  a  mixture  of  ferrous  and  ferric  sulphates  :  if  this 
yields  no  change,  the  hydrocyanic  acid  is  free ;  but  if  it  yields  Prus- 
sian blue,  either  at  once  or  after  the  addition  of  hydrochloric  acid, 
then  the  poison  exists  in  the  form  of  a  cyanide.  If  the  liquid  under 
examination  has  an  alkaline  reaction,  the  poison,  if  present,  will  of 
course  be  in  the  form  of  a  cyanide,  even  though  originally  added  iu 
its  free  state. 

Should  the  mixture  in  the  retort  evolve  either  hydrochloric  acid 
or  sulphuretted  hydrogen,  this  will  collect  with  the  distillate,  and  in- 
terfere with  the  reaction  of  the  silver  test ;  neither  of  these  substances, 
however,  would  prevent  the  normal  reaction  of  either  the  iron  or  the 
sulphur  test.  Hydrochloric  and  hydrocyanic  acids  may  be  separated 
by  redistilling  a  portion  of  the  distillate  with  powdered  borax  or 
carbonate  of  calcium,  which  will  retain  the  chlorine  compound,  but 
not  hydrocyanic  acid. 

Distillation  tciih  an  acid. — If  the  above  method  fail  to  reveal  the 
presence  of  the  poison,  the  contents  of  the  retort,  after  the  addition 
of  water  if  they  have  become  thick,  are  acidulated  with  sulphuric 
acid,  and  distilled  as  before.  Any  simple  cyanide  present  would 
now  evolve  the  whole  of  its  cyanogen  in  the  form  of  hydrocyanic 
acid.  Should  it  at  first  be  suspected  that  the  poison  existed  as  an 
alkaline  cyanide,  this  method  of  distillation  may  at  once  be  adopted. 
It  must  be  remembered,  however,  that  by  this  process  a  ferrocyanide, 


190  HYDROCYANIC   ACID. 

such  as  potassium  ferrocyanide,  or  yellow  prussiate  of  potash,  would 
also  evolve  prussic  acid ;  and  the  same  may  also  be  true,  if  the  dis- 
tillation is  continued  for  some  time,  in  regard  to  the  sulphocyanide 
of  potassium,  which  exists  in  small  proportion  in  human  saliva. 

The  source  of  the  poison  obtained  in  the  distillate  when  an  acid 
has  been  employed  may  be  determrned  by  treating  a  portion  of  the 
reserved  liquid,  after  filtration  if  necessary,  with  a  few  drops  of  hy- 
drochloric acid,  and  stirring  the  mixture  for  some  minutes,  and 
then  adding  a  solution  of  ferric  chloride.  If  the  liquid  thus  treated 
contained  a  simple  cyanide,  the  iron  reagent  will  produce  no  visible 
change,  since  the  cyanide  would  have  been  converted  by  the  hydro- 
chloric acid  added  into  a  chloride,  and  the  whole  of  the  prussic  acid 
evolved;  but  if  it  contained  a  ferrocyanide  or  a  sulphocyanide,  this 
will  remain,  and  yield  either  a  deposit  of  Prussian  blue  or  a  deep  red 
solution,  as  the  case  may  be.  As  commercial  cyanide  of  potassium 
is  liable  to  be  contaminated  with  ferrocyanide  of  potassium,  traces  of 
the  latter  might  be  present  in  poisoning  by  the  former. 

If  there  is  reason  to  suspect  that  free  hydrocyanic  acid  or  cyanide 
of  potassium  is  present  with  ferrocyanide  of  potassium,  they  may 
be  separated,  according  to  Otto,  in  the  following  manner.  The  mix- 
ture is  treated  with  a  solution  of  ferric  chloride  as  long  as  a  precipi- 
tate is  produced,  by  which  the  ferrocyanide  compound  will  be  con- 
verted into  Prussian  blue ;  sodium  carbonate  is  then  added,  until  the 
mixture  exhibits  an  alkaline  reaction,  then  tartaric  acid,  until  it  shows 
a  feebly  acid  reaction ;  it  is  then  distilled  in  the  ordinary  manner. 
By  this  method  ferrocyanide  of  potassium  yields  a  distillate  entirely 
free  from  hydrocyanic  acid,  since  it  is  retained  as  Prussian  blue, 
which  is  unaffected  by  the  distillation ;  but  when  hydrocyanic  acid 
or  an  alkaline  cyanide  is  present,  the  distillate  will  contain  the  poison 
in  its  free  state. 

This  process  is  admirably  adapted  for  the  separation  of  free  hy- 
drocyanic acid  from  a  ferrocyanide ;  but  when  the  poison  is  present 
in  the  form  of  an  alkaline  cyanide,  much  or  even  the  whole  of  it,  if 
only  in  small  quantity,  may  be  retained  as  Prussian  blue.  It  is  true 
that  ferric  chloride  produces  with  cyanide  of  potassium  at  first  only 
free  hydrocyanic  acid,  sesquioxide  of  iron,  and  chloride  of  potassium  • 
but  this  mixture  will  after  a  little  time  form  more  or  less  Prussian 
blue.  This  conversion  will,  of  course,  take  place  at  once  if  the  iron 
reagent  contains  a  ferrous  salt. 


SEPARATION  FROM  ORGANIC  MIXTURES.         191 

For  the  separation  of  free  hydrocyanic  acid,  cyanide  of  potassiniii, 
and  ferrocyanide  of  })ota8.siuni,  it  lias  also  been  proposed  to  distil  the 
mixture  without  the  addition  of  an  acid,  when  the  free  prussic  a'id 
would  pass  over  with  the  distillate;  the  residue  in  the  retort  is  then 
filtered,  and  the  filtrate  concentrated  to  a  small  volume  and  treated 
with  strong  hot  alcohol,  which  Ayill  dissolve  the  cyanide,  whilst  the 
ferrocyanide  would  be  precipitated  in  yellowish-white  scales,  it  being 
insoluble  in  this  liquid. 

For  the  detection  of  an  alkali  cyanide  in  the  presence  of  a  ferro- 
cyanide, W.  J.  Taylor  has  recently  advised  [Chem.  News, 'Nov.  1884, 
227)  to  distil  an  aqueous  solution  of  the  mixture  with  an  excess  of 
acid  sodium  carbonate,  when  the  cyanide  will  be  decomposed  with 
the  evolution  of  hydrocyanic  acid,  the  ferrocyanide  remaining  un- 
changed. The  evolved  hydrocyanic  acid  may  be  collected  in  a 
solution  of  ammonium  sulphide,  which  will  retain  it  as  ammonium 
sulphocyanide,  readily  recognized  by  its  reaction  with  ferric  chloride. 
According  to  this  author,  the  presence  of  potassium  sulphate,  potas- 
sium ferricyanide,  potassium  sulphocyanide,  or  of  ammonium  salts, 
does  not  interfere  with  the  reaction. 

From  the  Blood  and  Tissues. — The  methods  already  described  are 
equally  applicable  for  the  examination  of  any  of  the  fluids  or  soft 
solids  of  the  body,  in  poisoning  by  prussic  acid.  Experiments  upon 
animals  have  shown  that  the  poison,  when  introduced  into  the  stomach, 
may  be  diffused  throughout  the  blood  within  a  few  seconds.  In  the 
case  already  cited  from  Casper,  in  which  a  mixture  of  prussic  acid 
and  some  essential  oils  proved  fatal  to  a  woman,  the  distillate  ob- 
tained from  about  an  ounce  of  blood  from  the  body  gave,  with  rhe 
iron  and  sulphur  tests,  very  distinct  evidence  of  the  presence  of  the 
poison  :  the  silver  test  was  not  applied.  The  blood  was  treated  with 
a  small  quantity  of  spirits  of  wine  and  phosphoric  acid,  and  distilled 
until  about  two  drachms  of  fluid,  smelling  slightly  of  bitter  almonds, 
had  passed  over.  In  this  case,  death  must  have  taken  place  with 
great  rapidity,  since  the  deceased  was  found  lying  on  the  floor,  with 
half  a  cucumber  in  one  hand  and  a  water-jug  in  the  other.  The  same 
writer  relates  another  case,  in  which  an  apothecary  took,  with  suici- 
dal intent,  an  unknown  quantity  of  hydrocyanic  acid,  and  the  poison 
was  recovered  from  the  blood,  by  being  distilled,  in  this  instance, 
with  a  few  drops  of  sulphuric  acid.  It  was  also  found  in  the  con- 
tents of  the  stomach ;  but  not  in  the  urine  contained  in  the  bladder. 


192  HYDROCYANIC   ACID. 

Failure  to  detect  the  Poison. — On  account  of  its  rapidly- 
fatal  effects,  there  is  no  ordinary  poison  more  likely  than  hydrocyanic 
acid  to  remain  in  the  body  at  the  time  of  death ;  yet  on  account  of 
its  ready  decomposition  and  great  volatility,  there  is  perhaps  none 
that  may  more  rapidly  disappear  from  the  dead  body.  The  time  in 
which  a  given  quantity  of  the  poison  may  thus  entirely  disappear 
from  the  body,  or  from  any  organic  mixture,  will  of  course  depend 
upon  a  variety  of  circumstances.  In  a  case  of  suicidal  poisoning 
by  hydrocyanic  acid  mentioned  by  Prof.  Casper,  twenty-six  hours 
after  death  no  trace  of  the  poison  was  found  in  the  stomach,  but 
there  was  present  a  considerable  quantity  of  formic  acid,  as  a  result 
of  the  decomposition  of  the  prussic  acid. 

On  the  other  hand,  cases  are  recorded  in  which  the  poison  was 
recovered  after  comparatively  long  periods.  Thus,  Dr.  Christison 
quotes  a  case  in  which  it  was  detected  in  a  body  seven  days  after 
death,  although  the  corpse  had  never  been  buried,  and  had  been  for 
some  time  lying  in  a  drain.  In  an  instance  cited  by  Dr.  Taylor, 
where  a  dose  equivalent  to  something  over  three  grains  of  anhydrous 
prussic  acid  proved  fatal  in  about  fifty  minutes,  it  was  detected  both 
before  and  after  distillation,  in  the  contents  of  the  stomach,  seventeen 
days  after  death.  In  a  more  recent  case,  the  acid  is  said  to  have 
been  detected  in  the  blood  and  brain  eleven  days,  and  in  the  intestines 
fifteen  days,  after  death.  The  longest  period  in  this  respect  yet  re- 
ported is  in  a  case  in  which  E.  Reichardt  detected  hydrocyanic  acid 
two  months  after  death  in  a  case  of  undoubted  poisoning.  [Jour. 
Chem.  Soc.  Abst,  Feb.  1882,  246.)  In  this  instance  the  iron  and 
the  guaiacum-copper  tests  were  applied  to  the  distillate  from  the 
organs  after  addition  of  tartaric  acid,  the  absence  of  ferrocyanides 
and  thiocyanates  (sulphocyanides)  being  previously  determined. 

Quantitative  Analysis. — The  quantity  of  hydrocyanic  acid 
present  in  a  pure  solution  of  the  poison  may  be  readily  determined, 
by  precipitating  it  as  cyanide  of  silver.  For  this  purpose,  the  solu- 
tion is  treated  with  a  solution  of  silver  nitrate  as  long  as  a  precipitate 
is  produced ;  the  mixture  is  then  slightly  acidulated  with  a  few  drops 
of  nitric  acid,  and  the  precipitate  collected  on  a  filter  of  known 
weight,  thoroughly  washed,  dried  at  100°  C.  (212°  F.),  and  weighed. 
Every  one  hundred  parts  by  weight  of  cyanide  of  silver  thus  obtained 
correspond  to  20.15  parts  of  anhydrous  hydrocyanic  acid. 


piiosrnoRus.  193 

Section  III. — Phosphorus. 

JJiMori/. — This  loiiiarkable  elementary  substance  was  first  dis- 
covered by  Brandt,  in  1G69,  and  received  its  name  from  its  ready 
inflammability  and  from  being  luminous  in  the  dark.  Phosphorus 
is  found  in  the  three  kingdoms  of  nature,  but  most  abundantly  as 
a  constituent  of  bones,  in  which  it  exists  as  phosphoric  acid,  and 
this  in  combination  with  calcium  ;  it  is  never  found  in  its  free  state 
in  nature.  In  its  uncombined  state,  phosphorus  is  a  most  powerful 
poison,  and  numerous  instances  of  poisoning  by  it  have  occurred, 
especially  since  the  introduction  of  friction-matches,  and  of  phos- 
phorus-pastes for  the  ])urpose  of  destroying  rats. 

Symptoms. — The  more  usual  effects  produced  by  phosphorus, 
when  taken  in  poisonous  quantity,  are  a  feeling  of  lassitude  ;  gaseous 
eructations,  which  have  a  garlic-like  odor,  and  are  sometimes  lumi- 
nous in  the  dark  ;  burning  pain  in  the  stomach  and  bowels ;  nausea ; 
violent  vomiting;  sometimes  purging;  great  thirst;  cold  perspira- 
tions ;  great  anxiety ;  and  a  feeble,  irregular  pulse.  The  matters  first 
vomited  have  generally  an  alliaceous  odor,  and  evolve  white  fumes, 
which  shine  in  the  dark ;  similar  appearances  have  also  been  observed 
in  the  faeces,  which  have  even  contained  solid  particles  of  the  poison. 
The  abdomen  becomes  tender  to  the  touch ;  the  extremities  cold ; 
the  pulse  almost  imperceptible;  the  pupils  dilated  and  insensible; 
and  frequently  death  is  preceded  by  convulsions.  If  the  patient 
survive  two  or  three  days,  jaundice  generally  manifests  itself,  usually 
appearing  first  in  the  conjunctiva.  The  urine  is  generally  albu- 
minous and  much  diminished  in  quantity,  or  it  may  be  entirely 
suppressed. 

In  a  case  of  poisoning  by  this  substance  related  by  Dr.  Lewin- 
sky, in  which  a  girl,  aged  twenty-two  years,  swallowed  a  portion  of 
phosphorus  scraped  from  a  small  packet  of  lucifer-matches,  the 
following  symptoms  were  observed.  Soon  after  taking  the  poison, 
the  patient  experienced  a  sharp  burning  pain  in  the  abdomen,  fol- 
lowed by  vomiting  of  matters  which  were  observed  to  be  luminous 
while  being  ejected  from  the  stomach.  Some  hours  afterward,  she 
was  suffering  from  vomiting  and  purging;  but  no  odor  of  phos- 
phorus was  perceptible  in  the  excretions.  The  abdomen  was  swollen 
and  sensitive  on  pressure ;  the  tongue  white  and  moist ;  the  pulse 
normal,  and  the  intellect  clear.     Vomiting,  alternating  with   hic- 

13 


194  PHOSPHORUS, 

cough,  continued  unceasingly  until  the  third  day ;  but  the  purging 
ceased  on  the  second  day.  On  the  third  day,  there  were  signs  of 
jaundice;  the  urine  was  scanty  and  of  a  dark  color;  and  the  pupils 
were  widely  dilated,  and  nearly  insensible  to  light.  On  the  fourth 
day,  the  jaundiced  appearance  of  the  face  was  much  increased,  and 
there  was  collapse  and  great  restlessness,  with  extreme  thirst,  and  a 
weak,  quick  pulse ;  but  the  vomiting  had  abated,  a  small  quantity 
of  blood  only  being  thrown  up ;  convulsions  and  impaired  conscious- 
ness then  supervened,  and  death  occurred  on  the  sixth  day  after  the 
taking  of  the  poison.     {Brit,  and  For.  Iled.-Chir.  Rev.,  Oct.  1859.) 

In  contrast  with  the  above  case  may  be  cited  the  following, 
related  by  Prof.  Casper.  [Forensie  Medicine,  ii.  100.)  A  young 
lady,  aged  twenty  years,  took  at  six  o'clock  in  the  evening  at  least 
three  grains  of  phosphorus  in  the  form  of  the  officinal  electuary. 
Those  around  her  remarked  nothing  peculiar ;  and  during  the 
evening  she  wrote  a  letter.  Later  in  the  evening  she  seemed  to 
her  family  to  exhale  "sulphur"  (evidently  confounding  the  vapor 
of  sulphur  with  that  of  phosphorus-matches),  and  complained  that 
the  light  blinded  her,  but  made  no  complaint  whatever  of  pain. 
During  the  night,  which  she  passed  sleeplessly,  she  vomited  once, 
and  died  quite  peacefully  at  six  o'clock  in  the  morning,  just  twelve 
hours  after  taking  the  poison. 

The  following  case,  in  which  about  three  grains  of  phosphorus 
had  been  taken,  is  reported  by  Dr.  S.  0.  Habershon.  {Medico-Chir. 
Trans.,  1867,  87.)  A  woman,  aged  twenty-eight,  in  good  health, 
drank  by  mistake  a  mixture  containing  some  rat-poison.  Imme- 
diately after  taking  the  draught  the  woman  complained  of  severe 
burning  pain  in  the  mouth  and  throat ;  the  breath  was  phosphores- 
cent; violent  vomiting  and  purging  soon  followed.  In  two  hours 
these  symptoms  subsided,  and  there  was  neither  dyspnoea  nor  cough. 
On  the  morning  of  the  sixth  day,  she  was  seized  with  violent  pain 
in  the  loins ;  the  skin  was  moist,  but  the  face  and  extremities  were 
cold ;  the  conjunctiva  and  the  whole  body  were  slightly  jaundiced ; 
the  pupils  were  natural;  the  lips  parched;  the  tongue  dry.  The 
abdomen  was  somewhat  distended  and  tympanitic;  the  liver  was 
enlarged ;  no  pulse  could  be  felt  at  the  wrist.  Some  hours  later, 
sudden  vomiting  of  a  dark  grumous  fluid  came  on,  and  the  patient 
died  almost  immediately,  five  days  after  taking  the  poison. 

Dr.  F.  P.  Henry  has  recently  reported  a  case  (Medical  Times, 


PHYSIOLOGICAL   EFFECTS.  195 

Pliila.,  June,  1883,  696),  in  whicli  a  man,  aged  twenty-two,  drank 
a  solution  of  phospliorus  obtained  by  soaking  tlie  heads  of  a  box  of 
matolios  in  water.  Fifteen  minutes  after  swallowing  the  solution, 
the  patient  experieneed  a  burning  sensation  in  the  stomach,  whicii, 
after  a  time,  became  excruciating.  Copious  and  repeated  attacks  of 
vomiting  then  ensued,  and  there  was  excessive  thirst.  On  the  next 
day  there  was  a  loose  discharge  from  the  bowels.  These  symptoms 
were  followed  by  tenderness  over  the  liver ;  severe  pain  in  the  abdo- 
men ;  pulse  full  and  strong ;  and  the  urine  contained  considerable 
albumen.  Some  days  later,  there  was  intense  jaundice;  one  clay- 
colored  stool ;  and  the  bladder  was  relieved  by  catheter  of  forty- 
eight  ounces  of  urine,  which  contained  bile-pigment  in  large  quan- 
tity, and  had  the  odor  of  phosphorus.  The  man  died  one  week,  less 
fourteen  hours,  after  taking  the  poison. 

In  a  case  related  by  Dr.  Stevenson,  a  woman  took  a  quantity  of 
phosj^horus  estimated  at  something  less  than  two  grains,  and,  except 
slight  gastric  pain,  no  marked  symptoms  appeared  for  three  and  a 
half  days.  The  usual  symptoms  then  developed,' followed  by  death 
on  the  seventh  day.     [The  Practitioner,  Dec.  1882,  432.) 

A  singular  case  is  related  by  Dr.  Landerer,  in  which  a  woman, 
in  order  to  come  into  the  possession  of  a  large  inheritance,  poisoned 
a  boy,  aged  fifteen  years,  by  introducing  the  ends  of  phosphorus- 
matches  into  his  rectum.  The  boy  died  the  same  night,  with  severe 
pain  and  inflammation  of  the  rectum.  {3Iedical  J^ew-'i,  May,  1882, 
544  ;  from  Archiv  d.  Pharni.,  1882.) 

The  inhalation  of  the  vajMV  of  phosphorus  by  an  apothecary, 
who  applied  in  his  cellar  some  phosphorus-paste  to  some  Avheat  to  be 
used  for  the  destruction  of  field-mice,  caused  complete  prostration, 
and  death  within  a  week.     {Amer.  Jour.  Pharm.,  Jan.  1873,  16.) 

Period  when  Fatal. — In  fatal  poisoning  by  phosphorus,  death 
usually  takes  place  in  from  one  to  five  days.  One  of  the  most 
rapidly  fatal  cases  yet  recorded  is  that  related  by  Prof.  Casper,  cited 
above,  in  which  death  occurred  in  twelve  hours.  In  another  case,  the 
phos})horus  from  forty-two  matches  proved  fatal  in  thirteen  hours. 
And  in  a  case  quoted  by  Dr.  Christison,  the  taking  of  a  portion 
of  lucifer-match  composition  was  followed  by  vomiting,  pain  in 
the  abdomen,  anxiety,  restlessness,  excessive  thirst,  and  death  in  fif- 
teen hours.  {Op.  dt,  151. j  Dr.  Habershon  cites  a  case,  related  by 
Dr.  Tiingle,  fatal  in  half  an  hour.     In  an  instance  reported  by  Dr. 


196  PHOSPHORUS. 

Flachsland,  a  young  man,  aged  twenty-four  years,  took  an  unknown 
quantity  of  the  poison,  spread  on  bread  with  butter.  He  soon  ex- 
perienced violent  pain  in  the  stomach  and  bowels,  and  intense 
vomiting,  which  continued  the  following  day :  after  the  use  of 
clysters,  he  passed  small  fragments  of  phosphorus,  which  were  lu- 
minous in  the  dark  and  burned  spots  in  the  bed-linen.  Death  ensued 
in  forty  hours  after  the  poison  had  been  taken.  {Medizinisch- 
Chirurgische  Zeitung,  1826,  iv.  183.)  Orfila,  in  quoting  this  case 
{Toxicologie,  1852,  i.  84),  erroneously  states  that  death  took  place  in 
four  hours. 

Among  the  more  protracted  cases  may  be  mentioned  the  follow- 
ing. M.  DiiFenbach,  an  apothecary  of  Biel,  as  a  matter  of  experi- 
ment, took  one  grain  of  phosphorus  on  the  2d  of  July,  1823.  On 
the  21st  of  the  same  month  he  took  two  grains,  and  on  the  following 
day  increased  the  dose  to  three  grains.  During  the  evening  of  the 
last  day  he  experienced  uneasiness  and  a  sense  of  pressure  in  the  ab- 
domen. These  symptoms  were  succeeded  by  violent  and  incessant 
vomiting,  convulsions,  delirium,  and  partial  paralysis,  and  death 
ensued  on  the  29th  of  the  month,  or  the  seventh  day  after  the  last 
dose  of  poison  had  been  taken.  {Revue  MSdicale,  1829,  iii.  429.) 
In  another  case,  reported  by  Dr.  Concato,  life  was  prolonged  eleven 
days.  And  in  a  case  quoted  by  Dr.  Beck,  in  which  a  young  man 
took  one  grain  and  a  half  of  phosphorus,  death  did  not  occur  until 
the  twelfth  day  after  the  taking  of  the  poison.     {Med.  Jur.,  ii.  511.) 

Fatal  Quantity. — The  effects  of  a  given  quantity  of  phosphorus 
will  depend  much  upon  the  state  in  which  it  is  taken.  A  child,  two 
years  and  a  half  old,  died  from  swallowing  the  phosphorus  contained 
on  eight  friction-matches ;  and  a  child,  two  months  old,  is  said  to 
have  died  from  the  effects  of  two  such  matches.  (Wharton  and 
Stille,  3Ied.  Jur.,  505.)  The  quantity  of  the  poison  taken  in  the 
last-mentioned  instance  could  not  have  much  exceeded  the  fiftieth 
of  a  grain.  In  a  case  quoted  by  Dr.  Taylor,  one-eighth  of  a  grain 
destroyed  the  life  of  a  lunatic.  In  another  instance,  the  composition 
from  thirty  or  forty  lucifer-matches,  administered  with  milk,  proved 
fatal  to  a  woman  in  less  than  forty-eight  hours.  {London  Chem. 
News,  April,  1860,  207.)  Again,  Dr.  Christison  quotes  the  case  of 
a  patient,  affected  with  lead-palsy,  who  died  in  about  two  days  from 
the  effects  of  considerably  less  than  a  grain  of  the  poison,  taken  in 
the  form  of  an  emulsion. 


ANTIDOTES.  ]  97 

On  tlie  otlicr  hand,  a  case  is  related  in  whieli  a  oliild  swallowed 
nearly  a  teaspoon ful  of  pliospliorns-paste,  prepared  for  killing  rats, 
and,  under  the  free  administration  of  inaj^nesia,  entirelv  recovered. 
[U.  S.  Dkpen.,  1865,  644.)  The  quantity  of  pliosphorus  taken  in 
this  case  probably  exceeded  one  grain.  In  a  ciise  quoted  by  Dr. 
Taylor,  a  young  woman  swallowed  the  phosphorus  obtained  from 
about  three  hundred  matches— equal  to  rather  less  than  five  grains 
of  the  poison — and  recovered  without  any  very  severe  symptoms. 
{On  Poisons,  345.)  These  are  the  most  remarkable  instances  of  re- 
covery, after  the  taking  of  this  poison,  yet  recorded ;  in  fact,  very 
few  cases  of  recovery  have  as  yet  been  reported. 

Treatment.— If  there  is  not  already  free  vomiting,  it  should 
be  induced  by  the  exhibition  of  an  emetic,  sulphate  of  copper,  in  re- 
peated doses,  being  preferred  for  this  purpose.  Calcined  magnesia, 
suspended  in  large  draughts  of  any  demulcent  liquid,  may  then  be 
freely  administered :  this  may  serve  to  neutralize  any  oxide  of  phos- 
phorus remaining  in  the  stomach.  Instances  are  related  in  which 
this  treatment  was  employed  with  great  success.  It  has  been  pro- 
posed to  administer  the  magnesia  in  suspension  in  chlorine  water ; 
but  more  recent  experiments  on  animals  have  indicated  that  this  mix- 
ture has  no  special  advantage.  Since  phosphorus  is  somewhat  soluble 
in  fatty  substances,  the  administration  of  these  should  be  avoided. 
If  the  poison  has  passed  into  the  intestines,  purgatives  may  be  used 
with  advantao-e. 

As  an  antidote  in  acute  phosphorus  poisoning,  oil  of  turpentine 
has  been  advised,  and  the  results  of  numerous  experiments  upon 
animals  have  been  adduced  in  its  favor.  In  the  hands  of  other 
experimentalists,  however,  this  substance  has  proved  Avholly  inert. 
It  is  now  generally  admitted  that  only  certain  kinds  of  turpentine 
are  antidotal,  that  which  is  old  and  has  not  been  rectified  being  the 
most  efficient.  So,  also,  the  soluble  salts  of  copper  have  been  recom- 
mended. Phosphorus, "in  contact  with  a  solution  of  this  metal,  is 
quickly  coated  with  a  black  deposit,  said  to  be  a  phosphide  of  copper. 
Prof  Bamberger  claims  that  this  antidote  is  more  efficient  than  oil 
of  turpentine;  whereas  G.  H.  Roessingh,  from  repeated  experiments, 
holds  the  opposite  view.  {New  Sydenham  Soc,  1873,  440.)  Among 
other  agents  that  have  been  proposed  as  antidotes  may  be  mentioned 
animal  charcoal,  oxygenated  water,  peroxide  of  hydrogen,  and  the 
slow  injection  of  oxygen  into  the  veins. 


198  PHOSPHORUS. 

Post-mortem  Appearances. — The  contents  of  the  stomach 
have  in  some  instances  evolved  white  fumes,  having  an  alliaceous 
odor,  and  being  luminous  in  the  dark.  The  lining  membrane  of  the 
stomach  is  generally  much  inflamed,  and  has  even  presented  a  gan- 
grenous appearance ;  these  appearances  may  extend  throughout  the 
intestines,  which  are  often  much  contracted.  The  liver,  spleen,  and 
kidneys  are  often  highly  reddened,  the  lungs  gorged  with  blood,  the 
heart  empty,  and  the  brain  congested.  The  blood  throughout  the 
body  is  usually  dark-colored  and  remarkably  fluid. 

In  the  more  protracted  cases,  the  skin  frequently  presents  a  jaun- 
diced appearance,  and  there  is  generally  fatty  degeneration  of  the 
liver,  kidneys,  and  heart ;  this  change  may  extend  to  most  of  the  soft 
organs  of  the  body.  The  liver  is  generally  enlarged,  of  a  yellow 
color,  and  soft  and  inelastic;  in  some  cases  this  organ  was  found 
atrophied. 

In  the  case  fatal  in  twelve  hours,  related  by  Prof.  Casper,  forty- 
eight  hours  after  death  luminous  vapors  were  observed  to  issue  from 
the  vagina,  and  a  grayish-white  vapor  smelling  strongly  of  phos- 
phorus continuously  streamed  from  the  anus  !  A  very  distinct  odor 
of  phosphorus  also  came  from  the  mouth,  but  without  any  visible 
vapor.  The  stomach  itself  diffused  no  odor  of  phosphorus ;  and  no 
part  of  its  mucous  membrane  was  either  softened  or  corroded.  It 
contained  about  six  to  eight  ounces  of  a  bright  blood-like  fluid, 
mingled  with  coagulated  milk;  no  particles  of  phosphorus  could  be 
detected  in  the  stomach,  even  with  a  magnifying-glass.  The  intes- 
tines were  pale,  and  presented  nothing  abnormal.  The  blood  was 
dirty-red,  of  a  syrupy  consistency,  and  the  blood-corpuscles  were 
transparent  and  deprived  of  their  coloring-matter.  The  liver,  spleen, 
and  kidneys  were  congested.  The  bladder  was  of  a  livid  color,  and 
contained  about  a  tablespoonful  of  milky  urine.  The  lungs  contained 
but  little  blood,  and  the  heart  was  almost  completely  empty ;  but  the 
large  blood-vessels  contained  much  blood.  The  meninges  were  mod- 
erately congested,  and  the  brain  contained  more  blood  than  usual. 

In  Dr.  Lewinsky's  case,  in  which  death  occurred  on  the  sixth 
day,  the  stomach  was  filled  with  gas  and  a  blackish-brown  fluid ;  its 
mucous  coat  was  raised  from  beneath,  and  covered  with  a  thick 
mucus,  streaked  with  dark-brown  lines.  The  intestines  contained 
a  blackish-brown,  thin,  frothy  liquid.  The  bladder  was  contracted 
and  empty.     The  cavity  of  the  throat  contained  a  bloody,  frothy 


GENERAL   CHEMICAL   NATURE.  199 

minus,  which  extended  into  the  bronchial  tnbes.  The  hnigs  were 
covered  with  a  Haky  exn<lation.  The  heart  was  contracted,  and  its 
cavities  contained  Ihiid  blood  with  a  little  coagnlated  fibrin.  The 
structure  of  the  brain  was  free  from  blood,  but  the  ventricles  con- 
tained a  drachm  of  serum.  A  chemical  examination  of  the  stomach 
and  its  contents,  by  Dr.  Schauenstein,  showed  no  indication  of  the 
presence  of  phosphorus. 

In  the  case  reported  by  Dr.  Flachsland,  which  proved  fatal  in 
fortv  hours,  watery  blood  flowed  in  large  quantity  from  the  nostrils, 
and  also  from  the  first  incisions  made  into  the  skin  and  muscles  of 
the  abdomen.  The  stomach  and  bowels  externally  were  inflamed ; 
the  mucous  membrane  of  the  stomach  presented  a  gangrenous  inflam- 
mation, which  extended  into  the  duodenum ;  the  large  intestines 
were  contracted  to  the  size  of  the  little  finger.  The  mesenteric 
glands  were  hardened,  and  the  spleen  and  kidneys  inflamed. 

Dr.  Hall  Curtis  relates  a  case  (Boston  3Ied.  and  Surg.  Jour.^ 
April,  1876,  433)  in  which  a  man  took  a  quantity  of  rat-poison, 
and  died  from  its  effects,  under  the  usual  symptoms,  in  forty-six 
and  a  half  hours.  No  symptom  was  observed  until  eight  hours 
after  the  poison  had  been  taken,  when  the  man  experienced  slight 
pain  at  the  epigastrium.  At  the  autopsy,  the  heart  was  found  pale 
and  soft;  its  muscular  tissue  was  slightly  yellowish  and  soft,  but 
not  friable;  and  its  cavities  contained  considerable  soft-clotted  blood. 
The  liver  was  normal  in  size,  but  both  externally  and  internally  it 
■was  of  a  bright  golden-yellow  color.  The  kidneys  were  pale,  the 
tubules  indistinct,  with  a  yellowish  tinge  between  the  cortical  and 
medullary  portions.  The  brain  was  normal.  Neither  the  stomach 
nor  the  small  intestines  were  inflamed  or  congested.  Examined 
microscopically,  the  liver,  heart,  and  kidneys  were  found  in  a  state  of 
excessive  fatty  degeneration.  Phosphorus  was  found  in  the  stomach 
and  in  the  urine. 

•    Chemical  Properties. 

General  Chemical  Nature. — Phosphorus,  at  ordinary  tem- 
peratures, is  a  soft,  colorless,  transparent  solid,  having  a  waxy  ap- 
pearance, and  a  specific  gravity,  according  to  Schrotter,  of  1.83.  It 
fuses  at  a  temperature  of  about  44°  C.  (111°  F.),  and  boils  at  290°  C. 
(554°  F.).  When  exposed  to  the  air,  it  slowly  absorbs  oxygen,  and 
emits  white  fumes  of  phosphorous  oxide;  at  the  same  time  it  exhales 


200  PHOSPHORUS. 

a  peculiar  garlic-like  odor,  and  the  fumes  are  luminous  in  the  dark. 
Berzelius  believed  that  this  luminosity  was  due  to  the  volatilization 
of  free  phosphorus,  but,  according  to  Schr5tter,  it  is  due  to  the  com- 
bination of  the  phosphorus  with  oxygen.  {Chem.  Gaz.,  xi.  312.) 
This  oxidation,  and  consequently  the  luminosity,  are  prevented  by  the 
presence  of  the  vapor  of  ether,  alcohol,  turpentine,  and  of  certain 
other  liquids,  even  when  these  are  present  only  in  minute  quantity. 

Heated  in  the  open  air,  phosphorus  takes  fire  at  a  temperature  of 
about  60°  C.  (140°  F.),  and  burns  with  a  brilliant  white  light,  evolv- 
ing dense  white  fumes  of  phosphoric  oxide.  The  presence  of  certain 
oxidizing  agents  causes  it  to  inflame  at  much  lower  temperatures. 

Solubility. — Phosphorus  is  insoluble  in  water,  but  it  dissolves  to 
a  limited  extent  in  fixed  and  volatile  oils,  especially  by  the  aid  of 
heat.  It  also  dissolves  to  a  limited  extent  in  ether,  and  somewhat 
more  freely  in  hot  naphtha,  from  which,  however,  it  partially  sepa- 
rates on  cooling  in  rhombic  dodecahedral  crystals.  It  is  freely  solu- 
ble in  chloride  of  sulphur,  and  in  disulphide  of  carbon ;  five  parts 
of  the  latter  liquid  dissolve  one  of  phosphorus  (Graham).  It  is 
insoluble  in  hydrochloric  acid,  but  warm  nitric  acid  readily  oxidizes 
and  dissolves  it  in  the  form  of  phosphoric  acid. 

When  phosphorus  is  immersed  in  water  and  exposed  to  the 
action  of  light,  it  slowly  becomes  covered  with  a  white  opaque 
coating,  which,  according  to  H.  Rose,  is  nothing  more  than  pure 
phosphorus,  the  change  being  simply  due  to  a  change  in  its  state  of 
aggregation.  At  the  same'  time,  however,  a  little  of  the  phosphorus 
undergoes  oxidation,  and  is  dissolved  by  the  liquid. 

Varieties. — Of  the  several  allotropic  forms  of  phosphorus,  the 
Red  or  amorphous  variety  is  the  only  one  that  need  be  mentioned. 
This  form  is  obtained  by  heating  ordinary  phosphorus  in  an  atmos- 
phere of  carbonic  acid  or  of  any  gas  that  does  not  act  upon  it  chem- 
ically, when  after  a  time  it  will  become  converted  into  a  dark-red 
amorphous  mass,  from  which  any  unchanged  phosphorus  may  be 
dissolved  by  treating''the  mixture  with  disulphide  of  carbon. 

This  variety  of  phosphorus  differs  not  only  in  respect  to  its 
physical  properties,  but  also  in  regard  to  its  physiological  effects  and 
chemical  properties,  from  ordinary  phosphorus,  although  its  ultimate 
composition  is  precisely  the  same.  Thus,  it  is  destitute  of  odor,  and 
does  not  become  luminous  in  the  dark  until  heated  to  about  204°  C. 
(400°  F.).     Its  fusing  point  is  about  249°  C.  (480°  F.) ;  at  a  tem- 


SPECIAL   CHEMICAT-    PROPERTIES.  201 

perature  of  about  260°  C.  (500°  F.)  it  is  reconverted  into  ordinary 
phospiionis.  It  is  insoluble  in  disulpliidc  of  carbon,  trichloride  of 
sulphur,  other,  alcohol,  and  naphtha  ;  but  it  is  s[)arin<rly  soluble 
in  oil  of  turpentine.  Moreover,  from  experiments  on  animals,  it 
ajipcars  to  be  entirely  destitute  of  poisonous  properties. 

Special  Chemical  Properties.— The  physical  appearance  of 
phosphorus,  together  with  its  odor,  the  production  of  white  fumes 
when  exposed  to  the  air,  its  ready  inflammability,  and  its  phospho- 
rescence in  the  dark,  readily  serve  to  distinguish  it  in  its  solid  state, 
even  in  very  minute  quantity,  from  all  other  substances. 

When  a  mixture  containing  free  phosphorus  is  gently  heated, 
best  by  means  of  a  water-bath,  in  a  test-tube,  in  the  neck  of  which 
is  suspended  a  slip  of  filtering-paper  moistened  with  a  solution  of 
silver  nitrate,  the  vaporized  phosphorus  on  coming  in  contact  with 
the  silver  comj^ound  decomposes  it,  with  the  production  of  phos- 
phoric acid  and  the  elimination  of  metallic  silver,  which  imparts  to 
the  paper  a  brown  or  black  coloration.  A  very  minute  trace  of  the 
poison  will  thus  manifest  itself. 

Since,  however,  there  are  several  other  vapors  that  will  blacken 
a  solution  of  silver  nitrate,  this  change  taken  alone  would  not  prove 
the  presence  of  phosphorus.  That  the  result  is  really  due  to  the 
presence  of  phosphorus  may  be  determined  by  digesting  the  black- 
ened paper  with  a  small  quantity  of  hot  water,  precipitating  any 
undecomposed  nitrate  of  silver  present  by  hydrochloric  acid,  filtering, 
and  examining  the  concentrated  filtrate  for  phosphoric  acid,  in  the 
manner  hereafter  indicated. 

When  phosphorus  in  its  free  state  is  mixed  with  diluted  sul- 
phuric acid  and  zinc  in  a  test-tube,  or  in  any  convenient  vessel,  a 
portion  of  the  hydrogen  gas  evolved  by  the  action  of  the  acid 
and  zinc  unites  with  the  phosphorus  with  the  production  of  phos- 
phuretted  hydrogen  gas,  which  is  luminous  in  the  dark,  and  some- 
times spontaneously  inflammable.  A  very  small  quantity  of  phos- 
phorus will  in  this  manner  evolve  a  phosphorescent  gas  for  half  an 
hour  or  longer ;  and  when  the  experiment  is  performed  in  a  small, 
narrow  test-tube  and  in  a  perfectly  darkened  room,  or  better  at  night, 
the  least  visible  quantity  of  the  poison  will  yield  very  satisfactory 
flashes  of  light,  which  continue  to  be  produced  for  some  time. 

If  the  phosphuretted  hydrogen  thus  evolved,  together  with  the 
free  hydrogen,  be  conducted  through  a  drawn-out  tube,  and  ignited. 


202  PHOSPHOEUS. 

they  burn  with  a  greenish  flame  surrounded  by  a  delicate  blue  mantle. 
Pa])er  moistened  with  nitrate  of  silver  solution  and  exposed  to  the 
unignited  gas  is  immediately  blackened.  If  the  gas  be  conducted 
into  water,  it  gives  rise  to  white  fumes  as  it  escapes  from  the  liquid. 
With  a  solution  of  nitrate  of  silver,  it  gives  rise  to  phosphoric  acid, 
which  remains  in  solution,  and  a  black  precipitate,  consisting  of  a 
mixture  of  metallic  silver  and  phosphide  of  silver.  When  conducted 
into  a  solution  of  corrosive  sublimate,  it  produces  a  yellow  or  yel- 
lowish-white precipitate,  which,  according  to  H.  E-ose,  consists  of 
phosphide  and  chloride  of  mercury. 

1.  MitseherlicK s  Method. 

The  most  delicate  method  yet  proposed  for  the  detection  of  un- 
combined  phosphorus  is  that  first  pointed  out  by  E.  Mitscherlich. 
It  consists  in  distilling  the  substance  containing  the  phosphorus  with 
diluted  sulphuric  acid,  and  conducting  the  evolved  vapors  through 
a  glass  tube  surrounded  by  a  condenser.  The  vapor  of  phosphorus 
is  thus  condensed,  and  gives  rise  to  a  continuous  luminosity,  when 
observed  in  the  dark. 

For  the  application  of  this  method,  the  phosphorus  mixture,  after 
the  addition  of  water  if  necessary,  is  acidulated  with  sulphuric  acid 
and  placed  in  a  glass  flask,  A,  Fig.  2.  The  flask  is  connected  by 
means  of  an  exit-tube,  a,  with  a  delivery-tube,  6,  which  is  bent  at  a 
right  angle,  and  after  passing  through  a  glass  cylinder,  B,  filled  with 
cold  water,  terminates  in  a  drawn-out  point  within  a  small  bottle, 
which  serves  as  a  receiver.  The  condenser  may  be  readily  constructed 
by  taking  a  glass  tube,  about  twenty  inches  in  length  and  one  inch 
and  a  half  in  diameter,  and  closing  the  ends  with  good  corks,  the 
upper  of  which  has  three  perforations,  while  the  lower  has  one  for 
the  passage  of  the  delivery-tube :  the  condenser  is  supplied  with  cold 
water  from  the  reservoir,  C,  the  liquid  being  conducted  by  a  funnel- 
tube,  c,  to  the  bottom  of  tlie  condenser ;  the  warmed  water  is  carried 
off  from  the  surface  of  the  liquid  by  a  siphon,  d.  Having  thus 
adjusted  the  apparatus,  a  dark  screen  is  placed  between  the  flask  and 
the  condenser. 

On  now  gently  boiling  the  contents  of  the  flask,  while  a  stream 
of  cold  water  flows  through  the  condenser,  a  very  distinct  and  con- 
tinuous luminosity,  usually  some  inches  in  length,  will  be  observed 
in  the  dark  to  play  up  and  down  the  cooled  portion  of  the  delivery- 


NflTSf'IIERI-K  Il's   TEST. 


20.- 


tube.  The  phosphorus  tliu.s  distilled  collects  with  the  condensed 
nqncoiis  vapor  in  the  receiver,  and  imparts  to  the  liquid  a  stron.L' 
alliaceous  odor.  When  the  quantity  of  phosphorus  is  not  too  minute, 
a  portion  of  it  collects  in  the  receiver  in  tlie  form  of  small  f^lobules  ; 
a  portion  of  it,  however,  always  undcr<(0cs  oxidation  and  remains  in 
solution  in  the  distillate,  in  the  form  of  phosphorous  acid,  and  also, 


Fig.  2. 


MitsclieiHch's  apparatus  for  tbe  detection  of  phosphorus. 


sometimes,  as  phosphoric  acid.    The  true  nature  of  any  globules  thus 
obtained  may  be  determined  even  by  their  physical  properties. 

The  presence  of  phosphorous  acid  in  the  distillate  may  be  shown 
by  treating  the  filtered  liquid  with  a  solution  of  silver  nitrate  or  of 
mercuric  chloride ;  but  as  both  these  reagents  produce  precipitates 
with  various  kinds  of  organic  matter,  which  if  present  in  the  original 
mixture  might  distil  over,  it  is  always  best,  when  examining  a  sus- 
pected mixture,  to  convert  the  phosphorous  acid  into  phosphoric  acid 
before  testing.  For  this  purpose,  the  distillate  is  treated  with  a  few 
drops  of  nitric  acid,  concentrated  to  a  small  volume,  filtered  if  neces- 


204  PHOSPHORUS. 

sary,  and  then  examined  by  molybdate  of  ammonium  or  any  of  the 
other  tests  pointed  out  hereafter  for  the  detection  of  phosphoric  acid. 

When  in  the  examination  of  a  suspected  mixture  a  luminosity 
has  been  observed  during  the  distillation,  and  globules  of  phosphorus 
have  collected  in  the  receiver,  it  is  unnecessary  to  examine  the  con- 
densed liquid.  On  the  other  hand,  if  no  luminosity  or  globules  of 
phosphorus  have  been  obtained,  great  care  should  be  exercised  in 
regard  to  any  deductions  from  the  detection  of  a  mere  trace  of  phos- 
phoric acid  in  the  distillate,  since  it  may  have  been  carried  over 
mechanically  from  the  mixture  submitted  to  distillation.  It  may  be 
remarked  that  it  is  only  when  the  original  mixture  contains  unoxi- 
dized  phosphorus  that  a  luminosity  and  globules  of  phosphorus  will 
be  obtained,  as  neither  phosphorous  acid  nor  phosphoric  acid  yields 
either  of  these  results ;  nor  will  either  of  these  oxides  appear  in  the 
distillate,  even  when  present  in  the  original  mixture  in  large  quantity, 
unless  they  be  carried  over  mechanically  with  the  vapor  of  water. 

Delieaey  of  this  3Iethod. — Mitscherlich  distilled  five  ounces  of 
a  mixture  containing  the  fortieth  of  a  grain  of  pure  phosphorus, 
— that  is,  one  part  of  phosphorus  in  little  less  than  one  hundred 
thousand  parts  of  the  mixture, — and  the  luminosity  continued  until 
three  ounces  of  liquid  distilled  over,  which  required  about  half  an 
hour.  In  another  experiment,  he  distilled  five  ounces  of  a  mixture 
containing  one-third  of  a  grain  of  phosphorus,  and  obtained  such  a 
number  of  globules  of  phosphorus  in  the  distillate  that  one-tenth 
part  of  them  would  have  sufl&ced  to  establish  their  true  nature. 

In  one  of  our  own  experiments,  the  fiftieth  of  a  grain  of  phos- 
phorus was  distilled  with  two  thousand  fluid-grains  of  water,  acid- 
ulated with  sulphuric  acid.  As  soon  as  the  mixture  was  brought 
to  the  boiling  temperature,  a  phosphorescent  light  some  inches  in 
length  appeared  in  the  tube  within  the  condenser,  and  continued 
without  intermission  for  thirty-four  minutes,  at  which  time  the  dis- 
tillation was  stopped,  and  eighteen  hundred  and  twenty  grains  of 
fluid  had  distilled  over.  The  distillate  had  a  strong  alliaceous  odor, 
but  it  contained  no  globules  of  phosphorus ;  it,  however,  readily  fur- 
nished evidence  of  the  presence  of  oxides  of  phosphorus.  The 
amount  of  phosphorus  that  passed  through  the  tube  per  second,  in 
this  experiment,  must  have  been  something  less  than  the  l-100,000th 
of  a  grain ;  yet  this  gave  a  luminosity  many  times  greater  than  would 
have  sufficed  to  recognize  its  presence  with  absolute  certainty. 


HYDROGEN   TEST.  205 

Interferences. — It  has  already  been  remarked  that  the  presetice  of 
certain  vaj^ors  may  entirely  prevent  the  himinosity  of  phosphorus. 
Thus,  if  the  mixture  subjected  to  distilhition  contained  ah;ohol,  ether, 
or  oil  of  turpentine,  no  luminosity  would  Ik;  obseived  as  long  as  these 
distilled  over.  Alcohol  and  ether,  beiui;-  very  volatile,  would  soon 
be  separated,  and  the  light  would  then  ai)j)ear;  but  this  would  not 
be  the  case  in  regard  to  the  presence  of  oil  of  turpentine  :  tlii-;  liquid, 
however,  is  not  likely  to  be  present  in  a  medico-legal  examination  for 
{)hosi)horus,  unless  it  had  been  given  as  an  antidote.  M.  Lipowitz 
has  shown  that  the  phosphorescence  is  also  interfered  with  by  the 
presence  of  ammonia;  but  this  substance  would  be  neutralized  by 
the  sulphuric  acid  added. 

According  to  Dr.  F.  Hoffman,  who  has  made  a  series  of  over  one 
hundred  and  fifty  experiments  after  Mitscherlich's  method,  the  reac- 
tion is  not  interfered  with  by  the  presence  of  either  tartar  emetic, 
magnesia,  oxide  of  iron,  musk,  castor,  opium,  albumen,  any  of  the 
metallic  salts,  volatile  organic  acids,  nor  by  free  acids ;  but  it  is  in- 
terfered with  or  entirely  prevented  by  iodine,  calomel,  and  corrosive 
sublimate  in  large  quantity,  and  metallic  sulphides  in  the  presence  of 
free  sulphuric  acid,  and  particularly  oil  of  wormseed.  [London  Chem. 
News,  Jan.  1861,  50.)  The  same  observer  remarks  that  numerous 
experiments,  by  distilling  the  brain  of  various  animals,  blood,  albu- 
men, casein,  fibrin,  legumen,  and  other  proteine  compounds,  with 
dilute  sulphuric  acid,  failed  to  yield  the  least  phosphorescence. 

2.  Hydrogen  Method. 

This  method,  first  devised  by  L.  Dusart  and  since  improved  by 
Fresenius,  is  based  upon  the  property  possessed  by  free  phosphorus, 
and  the  lower  oxides  of  phosphorus,  of  forming  with  nascent  hydro- 
gen phosphuretted  hydrogen,  which  burns  with  a  greenish  flame. 
The  color  of  the  flame  is  not  diminished  in  intensity  by  conducting 
the  mixed  gases  over  hydrate  of  potassium  or  caustic  lime :  these 
latter  substances  would  retain  any  sulphuretted  hydrogen  present, 
which  burns  with  a  blue  flame  and  thus  interferes  with  the  phos- 
phorus reaction. 

An  ordinary  gas-evolution  flask  is  charged  with  pure  diluted 
sulphuric  acid  and  zinc,  and  the  evolved  hydrogen,  after  being 
conducted  over  pumice-stone  moistened  with  a  saturated  solution  of 
caustic  potash,  ignited  as  it  escapes  from  a  drawn-out  tube  provided 


206  PHOSPHORUS. 

with  a  platinum  burner.  If  the  gas  burns  with  a  colorless  flame, 
the  phosphorus  mixture  is  introduced  by  means  of  a  funnel-tube 
into  the  flask,  when  the  evolved  gas  will  burn  with  a  characteristic 
green  color,  which  disappears  if  the  tube  becomes  heated.  For  this 
reason  the  end  of  the  tube  should  be  surrounded  with  moistened 
cotton.  If  a  piece  of  cold  porcelain  be  depressed  in  the  flame,  the 
latter  burns  with  an  emerald-green  color  at  the  points  of  contact 
until  the  porcelain  becomes  heated. 

On  following  this  method,  L.  Dusart  obtained  from  about  the 
sixth  of  a  grain  of  the  paste  of  matches  a  flame  that  not  only 
burned  for  an  hour  and  a  half  with  a  visible  green  tint,  but  also  pro- 
duced on  porcelain  spots  of  a  yellowish-red  color,  which  resembled 
finely  reduced  phosphorus.  {Jour,  de  Chim.  Med.,  1863,  663.)  The 
evolved  gas  has  a  peculiar  odor,  and  is  luminous  in  the  dark.  The 
peculiar  odor  of  hydrogen  when  obtained  from  iron  and  dilute 
acids,  according  to  Dusart,  is  due  to  the  presence  of  phosphuretted 
hydrogen. 

The  phosphide  of  silver  yields  by  this  method  the  same  results 
as  free  phosphorus.  The  silver  compound  may  be  obtained  by  gently 
heating  the  phosphorus  mixture,  acidulated  with  sulphuric  acid,  for 
some  hours  in  a  flask  through  which  a  slow  stream  of  carbonic  acid 
gas  is  being  passed,  and  collecting  the  evolved  vapor  in  a  solution 
of  nitrate  of  silver.  In  this  operation,  the  vaporized  phosphorus 
passes  through  the  atmosphere  of  carbonic  acid  without  undergoing 
any  change ;  but  on  coming  in  contact  with  the  silver  solution  it 
gives  rise  to  solid  phosphide  of  silver  and  free  phosphoric  acid.  The 
phosphide  of  silver  is  collected  and  washed  on  a  filter,  which  has 
previously  been  washed  in  diluted  nitric  acid  and  water ;  it  is  then 
suspended  in  a  little  water  and  introduced  into  the  hydrogen  appa- 
ratus. The  presence  of  phosphoric  acid  in  the  filtrate,  separated 
from  the  silver  compound,  may  be  determined  in  the  manner  hereto- 
fore indicated. 

Fresenius  states  that  he  obtained  by  this  process  the  clearest 
evidence  of  the  presence  of  phosphorus  in  a  large  quantity  of  putrid 
blood  mixed  with  the  composition  scraped  from  the  tip  of  a  common 
lucifer-match,  and  this  even  in  the  presence  of  substances  which 
prevent  the  luminosity  of  the  phosphorus  in  experiments  by  Mit- 
scherlich's  method. 


PHOSPIIORKJ   AflD.  207 

3.  Lipowitz's  Method. 

This  iiiethod  is  based  upon  the  j)roperty  possessed  by  sulplmr 
when  heated  with  free  pho,si)h()ru.s  of  combininjr  with  it,  even  when 
present  in  very  eomplex  mixtures  and  in  a  liighly  comminuted  state, 
and  producing  a  compound  in  whicli  the  presence  of  the  poison  is 
readily  determined.  The  phosphorus  mixture,  slightly  acidulated 
with  sulphuric  acid,  is  gently  boiled  for  about  half  an  hour  in  a 
retort  with  a  few  small  pieces  of  sulphur,  the  distillate  being  col- 
lected in  an  ordinary  receiver. 

The  fragments  of  sulphur  are  then  separated  from  the  cooled 
mixture  and  washed  with  water.  They  will  now  emit  the  peculiar 
odor  of  phosphorus,  and  be  luminous  in  the  dark.  When  gently 
heated  with  strong  nitric  acid,  they  yield  a  solution  containing  phos- 
phoric acid,  together  with  more  or  less  sulphuric  acid.  The  presence 
of  phosphoric  acid  in  this  mixture  may  be  shown  by  evaporatino- 
the  liquid  to  a  small  volume,  diluting  with  a  little  water,  filtering, 
neutralizing  the  filtrate  with  ammonia,  and  applying  the  magnesium 
test  hereafter  described. 

The  liquid  that  distils  over  into  the  receiver  will  usually  contain 
one  or  more  of  the  oxides  of  phosphorus,  and  have  an  alliaceous 
odor.  When,  however,  only  a  minute  quantity  of  phosphorus  is 
present  in  the  original  mixture,  the  whole  of  it  may  be  retained 
by  the  sulphur. 

By  this  method,  Lipowitz  states  that  he  detected  phosphorus  in 
complex  organic  mixtures  containing  only  the  l-140,000th  of  their 
weight  of  the  poison. 

Since  in  medico-legal  investigations  for  phosphorus  it  often  be- 
comes necessary  to  recover  the  poison,  in  part  at  least,  as  phosphoric 
acid,  before  describing  the  methods  of  separating  the  former  from 
organic  mixtures  the  general  nature  and  chemical  properties  of  the 
latter  will  be  considered. 

Phosphoric  Acid. 

General  Chemical  Nature. — Anhydrous  phosphoric  acid, 
or  phosphoric  oxide,  is  a  compound  of  two  atoms  of  phosphorus  Avith 
five  atoms  of  oxygen,  P2O5;  it  is  the  highest  oxide  of  phosphorus 
known.     In  its  anhydrous  state  it  forms  a  snow-white  amorphous 


208  PHOSPHOEIC   ACID. 

mass,  which  has  a  strong  affinity  for  water,  and  rapidly  deliquesces 
when  exposed  to  the  air,  forming  a  hydrate.  Monohydrated  phos- 
phoric oxide  is  usually  prepared  by  boiling  phosphorus  with  diluted 
nitric  acid,  and  evaporating  the  solution  until,  on  cooling,  it  solidifies 
to  a  hard  transparent  mass;  in  this  state  it  is  known  as  glacial 
johosphoric  acid,  or  metaphosphorie  acid,  and  has  the  composition 

H20,PA5  or  HPO3. 

Phosphoric  oxide  also  unites  with  two  and  with  three  molecules 
of  water,  forming  respectively  pyrophosphoric  acid,  2H2O ;  PgOj,  and 
orthophosphoric  acid,  SHgO ;  P2O5.  The  last-mentioned  is  the  ordi- 
nary phosphoric  acid,  and  is  usually  represented  by  the  formula 
H3PO,;  thus:  3H2O;  P205=2H3p6,. 

Common  phosphoric  acid,  or  orthophosphoric  acid,  is  capable  of 
forming  three  series  of  salts,  according  as  one,  two,  or  all  three  of 
its  atoms  of  hydrogen  are  replaced  by  a  metal ;  it  is  therefore  tribasic. 
The  salts  of  this  acid,  except  those  of  the  alkalies,  are  insoluble  in 
water ;  but  they  are  freely  soluble  in  the  presence  of  a  free  acid,  even 
in  most  instances  of  acetic  acid. 

Special  Chemical  Properties. — In  the  following  investiga- 
tions of  the  reactions  of  reagents  with  solutions  of  phosphoric  acid, 
the  latter  was  employed  in  the  form  of  common  phosphate  of  sodium. 
The  fractions  indicate  the  amount  of  phosphoric  oxide  in  solution  in 
one  grain  of  water ;  the  results,  unless  otherwise  stated,  refer  to  the 
behavior  of  one  grain  of  the  solution. 

1.  Silver  Nitrate. 

This  reagent  fails  to  produce  a  precipitate  in  solutions  of  free 
phosphoric  acid ;  but  in  neutral  solutions  of  the  alkaline  phosphates 
it  occasions  a  light-yellow  precipitate  of  tribasic  phosphate  of  silver, 
AggPO^.  The  precipitate  is  readily  soluble  in  ammonia,  and  also  in 
nitric,  acetic,  and  free  phosphoric  acids ;  hydrochloric  acid  changes  it 
to  white  chloride  of  silver.  From  dilute  solutions,  the  formation  of 
the  precipitate  is  much  facilitated  by  the  aid  of  a  gentle  heat. 

1.  _i^  grain  of  phosphoric  oxide,  in  one  grain  of  water,  yields  a 

copious  yellow  deposit,  which  remains  amorphous. 

2.  Yinro"  gi'ain  yields  a  very  good  precipitate. 

3.  yQ-i^-Q-  grain :  a  very  satisfactory  deposit,  of  a  very  pale  yellow 

color.     The  precipitate  from  ten  grains  of  the  solution  has  a 
very  satisfactory  yellow  color. 


MAGNESIUAf   TliST.  209 

4-  Tnr.VriT  gi''i'"  :  aitcr  a  very  little  time,  a  quite  distinct  cloiidiness 
appears.     Ten  grains  of  the  solution  yield  a  very  satisfactory 
turbidity,  hut  the  yellow  color  is  not  apparent. 
Nitrate  of  silver  also    throws  down   from    neutral   solutions  of 
arsenious  acid  a  yellow  preci])itate,  which,  however,  usually  becomes 
crystalline.    The  arsenical  precipitate,  like  that  from  phosphoric  acid, 
is  readily  soluble  in  ammonia  and  in  free  acids;  but  when  dried,  and 
heated  in  a  reduction-tube,  it  yields  a  sublimate  of  octahedral  crystals 
of  ai-senious  oxide,  in  which  it  is  readily  distinguished  from  the  phos- 
phorus compound.     The  reagent  produces  yellowish-white  precipi- 
tates in  solutions  of  iodides  and  of  bromides;  but  these  precipitates 
are  insoluble  in  dilute  nitric   acid,  and  only  sparingly  soluble  in 
ammonia. 

2.  Magnesium  Sulphate. 

This  reagent  throws  down  from  strong  solutions  of  the  alkaline 
phosphates,  but  not  of  free  phosphoric  acid,  a  white  amorphous  pre- 
cipitate of  phosphate  of  magnesium,  MgHPO^,Aq.  The  quantity  of 
the  precipitate  is  much  increased  by  boiling  the  mixture,  it  then  having 
the  composition  Mg32P04,2iAq.  One  grain  of  a  1-lOOth  solution 
of  phosphoric  oxide,  in  the  form  of  an  alkaline  phosphate,  yields  a 
very  good  precipitate  without  the  application  of  heat.  Ten  grains 
of  the  same  solution  yield,  upon  boiling  the  mixture,  a  very  copious 
deposit.  Ten  grains  of  a  1-lOOOth  solution  remain  clear  on  the 
addition  of  the  reagent,  but  when  the  mixture  is  boiled  it  yields  a 
quite  good  flocculent  precipitate. 

A  mixture  of  magnesium  sulphate,  ammonium  chloride,  and  free 
ammonia  produces  in  solutions  of  free  phosphoric  acid  and  of  alka- 
line phosphates  a  white  crystalline  precipitate  of  ammonium  mag- 
nesium phosphate,  NH,MgP0„6Aq.  This  reaction  is  much  more 
delicate  and  characteristic  than  that  produced  by  magnesium  sulphate 
alone.  The  formation  of  the  precipitate  from  very  dilute  solutions 
is  much  fticilitated  by  stirring  the  mixture  with  a  glass  rod.  The 
precipitate  is  readily  soluble  in  free  acids,  but  insoluble  in  ammonia, 
even  more  so  than  in  pure  water. 

1-  TW  g''ai»  of  phosphoric  oxide,  when  treated  with  the  above  mix- 
ture, yields  a  very  copious,  gelatinous  precipitate,  which  in  a 
little  time  becomes  crystalline. 
-•  TWO  gi'^i"  :  a  copious  precipitate,  which  immediately  begins  to 


14 


210  PHOSPHORIC   ACID. 

crystallize,  and  soon  becomes  entirely  converted  into  feathery 
and  stellate  crystals,  Plate  IV.,  fig.  3. 

3.  ^QQQ    grain :    an   immediate  crystalline   precipitate,  which    soon 

becomes  rather  abundant.  , 

4.  To". Wo  gi'ai'3  yields  an  immediate  cloudiness,  and  in  a  little  time 

a  crystalline  deposit. 

5.  2T.Wo' S™^  •  ^^  ^  ^^^y  little  time  the  mixture  becomes  turbid, 

and  crystals  can  be  seen  by  the  microscope ;  after  a  few  minutes 
there  is  a  quite  satisfactory  crystalline  deposit. 

6.  -g-o.Voo"  gi'^i"  •  after  a  few  minutes  crystals  appear  to  the  micro- 

scope, and  after  some  minutes  they  are  quite  obvious  to  the 
naked  eye. 

7.  ToT^TTo  graiii  •  after  about  fifteen  minutes  crystals  are  perceptible 

to  the  naked  eye. 
This  reagent  mixture  also  produces  a  similar  crystalline  precipi- 
tate in  solutions  of  arsenic  acid.  When,  however,  the  arsenical  pre- 
cipitate is  dissolved  in  just  sufficient  acetic  acid,  and  the  solution 
treated  with  nitrate  of  silver,  it  yields  a  reddish-brown  deposit; 
whereas  the  phosphoric  precipitate,  when  treated  in  the  same  man- 
ner, yields  a  white  deposit.  The  same  reddish-brown  precipitate  is 
produced  by  nitrate  of  silver  from  normal  solutions  of  arsenic  acid. 

3.  Molybdate  of  Ammonium. 

The  test-fluid  is  prepared  by  treating  a  solution  of  ammonium 
molybdate  with  sufficient  nitric  acid  to  redissolve  any  precipitate  that 
first  forms;  or,  according  to  Sonnenschein,  who  first  proposed  the 
test,  one  part  of  molybdic  acid  is  dissolved  in  eight  parts  of  ammonia 
solution,  and  this  solution  slowly  added  to  twenty  parts  of  nitric 
acid.  Recently  (1882),  Kupfierschlager  has  advised  to  dissolve  ten 
parts  of  molybdic  acid  in  fifteen  parts  of  aqua  ammonige  previously 
diluted  with  thirty  parts  of  water,  and  add  the  solution  little  by  little 
to  one  hundred  parts  of  nitric  acid  of  specific  gravity  1.20.  After 
a  few  days  the  clear  liquid  is  decanted  and  ready  for  use.  • 

To  apply  the  test,  a  small  quantity  of  the  test-fluid  is  placed  in 
a  test-tube,  and  a  few  drops  of  the  phosphoric  acid  solution  added, 
when,  if  the  reagent  is  greatly  in  excess,  the  mixture  will  acquire 
a  yellow  color  and  yield  a  yellow  pulverulent  precipitate  of  ammo- 
nium phosphomolybdate.  From  very  dilute  solutions  of  the  acid 
the  precipitate  is  slow  to  appear;    the  reaction  is  greatly  promoted 


MOLYBDIC   ACID   TEST.  211 

by  a  gentle  heat.  Accordincr  t„  M.  Seligsolin,  the  precipitate  con- 
tains only  3.14  per  cent,  of  phosphoric  oxide,  its  (;()inposition  being 
6OM0O3;  4{3NI-I,;  PO,);  1511,0:  diflcrent  fonnulic,  however,  liave 
been  assigned  to  its  composition. 

Ill  the  presence  of  excess  of  the  reagent,  ammonium  phospho- 
molybdate  is  insohible  in  nitric,  hydrochloric,  and  most  other  acids 
even  on  boiling;  but  it  is  readily  soluble  in  excess  of  free  phos- 
phoric acid  and  of  alkaline  phosphates,  the  caustic  alkalies  and  their 
carbonates,  and  in  the  alkaline  tartrates.  (Chem.  Gaz.  x  1852 
216,390.) 

In  examining  the  limit  of  the  reaction  of  this  test,  one  grain  of 
the  phosphoric  acid  solution  was  added  to  five  fluid-grains  of  the 
test-fluid,  placed  in  a  small  test-tube. 

1-  TOTo   gi'-^i"   of  phosphoric  oxide  produces  an   immediate  yellow 

solution  and  a  bright  yellow  precipitate,  which  in  a  little  time 
becomes  quite  copious.  The  precipitate  is  much  increased  in 
quantity  by  warming  the  mixture. 

2-  TWO  gi'ain  :  the  mixture  immediately  assumes  a  yellow  color,  and 

in  a  little  time  yields  a  copious  yellow  deposit.  If  the  precipi- 
tate be  dissolved  in  the  mixture  by  excess  of  ammonia,  and  then 
a  mixture  of  sulphate  of  magnesium  and  chloride  of  ammonium 
added,  it  yields  an  immediate  crystalline  precipitate  of  ammo- 
nium magnesium  phosphate,  not  to  be  distinguished  from  that 
thrown  down  from  a  pure  solution  of  phosphoric  acid  of  the 
same  strength. 

3-  Tir.W  g^'ain  :  the  mixture  immediately  assumes  a  yellow  tint, 

which  increases  in  intensity,  and  in  a  little  time  a  yellow  pre- 
cipitate separates.  Upon  gently  heating  the  mixture,  it  yields 
a  good,  yellow  deposit. 

4-  Fo.WiJ  grain :  after  a  little  time  the  mixture  acquires  a  yellow 

tint;  by  heat  the  yellow  color  becomes  very  distinct,  and  yellow 
flakes  separate.  These  gather  upon  the  surface  of  the  fluid  and 
form  an  adherent,  yellow  pellicle. 
^-  nnLoTTT  grain  :  after  several  minutes,  no  perceptible  chauo-e.  But 
if  the  mixture  be  heated,  it  assumes  a  distinctly  yellow  color, 
and  after  a  time  small  yellow  flakes  appear  upon  the  surface  of 
the  liquid. 

This  reagent  also  produces  a  yellow  coloration  and  precipitate  in 
solutions  of  arsenic  acid,  but  only,  however,  as  first  pointed  out  by 


212  PHOSPHORUS. 

Sonnenschein,  when  the  mixture  is  heated  to  about  the  boiling  tem- 
perature. The  absence  of  this  acid  may  be  shown  by  nitrate  of 
silver,  in  the  manner  already  indicated.  So,  also,  on  the  application 
of  heat,  the  reagent  imparts  a  yellow  color  to  solutions  of  siliciG  add; 
but  this  substance  yields  no  precipitate,  nor  does  it  even  yield  a  yellow 
coloration,  unless  the  mixture  be  heated. 

Other  Reactions. — Phosphoric  acid  is  also  precipitated,  at  least 
from  neutral  solutions,  by  acetate  of  lead,  soluble  salts  of  barium, 
strontium,  calcium,  and  of  several  other  metals.  The  lead  precipitate 
is  almost  wholly  insoluble  in  acetic  acid,  but  most  of  the  other  pre- 
cipitates are  readily  soluble  in  this  acid.  These  reactions,  however, 
are  common  to  solutions  of  several  other  acids,  and  in  most  instances 
are  much  inferior  in  delicacy  to  the  tests  already  mentioned. 

Separation  from  Organic  Mixtures. 

The  odor  emitted  by  phosphorus  is  so  peculiar  that  it  will  often 
serve  to  detect  the  poison  with  considerable  certainty,  even  when 
present  in  very  complex  mixtures.  It  must  be  remembered,  how- 
ever, that  the  presence  of  other  odors  may  entirely  conceal  that  of 
this  substance,  especially  if  it  is  present  only  in  minute  quantity. 
We  have  even  found  this  to  be  the  case  wdien  comparatively  large 
quantities  of  the  poison  were  purposely  added  to  animal  mixtures 
which  were  undergoing  decomposition.  According  to  Dr.  F.  Hoff- 
man [Chem.  News,  iii,  50),  coffee,  mustard,  smoked  meat,  highly- 
seasoned  food  and  beverages,  and  medicines  containing  odorous 
gum-resins,  volatile  oils,  musk,  castor,  camphor,  and  chlorine,  have 
the  property  of  concealing  the  odor  of  the  poison,  at  least  if  present 
only  in  minute  quantity. 

Organic  mixtures  containing  free  phosphorus,  when  exposed  to 
the  air,  usually  evolve  vapors  which  are  luminous  in  the  dark, 
especially  if  the  mixture  be  gently  heated  and  stirred.  If  on  thus 
examining  the  mixture  any  solid  particles  of  the  poison  are  found, 
they  may  be  washed  in  water,  then  in  alcohol,  and  preserved  for 
future  examination  if  necessary.  If  the  mixture  under  examina- 
tion is  ammoniacal  from  putrefaction,  before  being  examined  in  re- 
gard to  its  luminosity  it  should  be  acidulated  with  sulphuric  acid. 
Should  these  means  fail  to  prove  the  presence  of  the  poison,  the  sus- 
pected mixture  is  examined  by  one  or  other  of  the  following  methods. 


SEPARATION    FROM    ORGANIC   MIXTURES.  213 

MitscherUcli' X  Method. — A  comparatively  large  portion  of  the 
niixturo,  acidulated  with  sulphuric  acid,  may  be  examined  after  this 
method.  A.s  this  is  the  most  satisfactory  ])r()cess  yet  proposed  for 
ihe  detection  of  free  piiosphorus,  it  should  never  be  omitted,  unless 
the  poison  has  already  been  discovered  in  its  solid  state.  If  during 
the  tlistiliation  the  contents  of  the  flask  become  thick,  they  should 
be  diluted  with  water,  and  the  process  continued  as  long  as  any 
luminosity  appears  in  the  condensing-tube.  If  the  distillate  thus 
obtained  contains  any  globules  of  phosphorus,  they  are  carefully 
separated  from  the  liquid,  then  washed,  dried  between  folds  of  bibu- 
lous paper,  and  weighed.  The  liquid  may  then,  after  the  addition 
of  a  few  droi)s  of  nitric  acid,  be  concentrated  to  a  small  volume,  and 
a  portion  of  it  examined  by  molybdate  of  ammonium  for  phosphoric 
acid  ;  another  portion  may  be  neutralized  with  ammonia,  and  then 
treated  with  a  mixture  of  magnesium  sulphate  and  ammonium 
chloride,  which  will  precipitate  any  phosphoric  acid  present  as 
ammonium  magnesium  phosphate. 

When  this  method  yields  a  distinct  luminosity  or  furnishes  glob- 
ules of  phosphorus,  it  is  certain  that  the  poison  was  present  in  its 
free  state.  Should,  however,  the  phosphorus  have  already  undergone 
oxidation,  this  method  will  yield  no  evidence  of  its  presence.  Under 
these  circumstances,  the  remaining  contents  of  the  flask  are  examined 
for  oxides  of  phosphorus,  in  the  manner  described  hereafter.  It 
must  also  be  borne  in  mind  that  the  luminosity  may  be  entirely 
prevented  by  the  presence  of  certain  volatile  substances.  These 
substances,  however,  would  not  prevent  any  free  phosphorus  present 
from  passing  over  into  the  receiver,  and  there  appearing  at  least  in 
the  form  of  an  oxide.  That  the  luminosity  of  phosphorus  is  not 
readily  interfered  with  by  the  ordinary  products  of  decomposition  is 
shown  by  the  following  experiment. 

The  putrid  mass  resulting  from  exposing  a  human  stomach  with 
its  contents,  free  from  phosphorus,  to  the  action  of  the  air  for  six 
weeks,  was  made  into  a  thin  paste  by  the  addition  of  water.  Twenty- 
five  hundred  fluid-grains  of  this  highly  offensive  mixture,  acidulated 
with  sulphuric  acid,  were  then  distilled  with  about  the  thirtieth 
of  a  grain  of  phosphorus,  added  in  a  finely  divided  state.  Nearly 
as  soon  as  the  mixture  reached  the  boiling  temperature  a  very  dis- 
tinct phosphorescence  appeared  within  the  condenser,  and  continued 
without  interruption  for  twenty-six  minutes,  when,  the  contents  of 


214  PHOSPHORUS. 

the  flask  having  become  veiy  thick  and  black,  the  distillation  was 
discontinued.  The  distillate  thus  obtained  measured  nearly  eighteen 
hundred  fluid-grains,  had  a  milky  appearance  and  very  offensive 
odor,  but  no  odor  or  globules  of  phosphorus  were  detected.  TThen, 
however,  this  liquid  was  treated  with  a  few  drops  of  nitric  acid,  and 
evaporated  to  a  small  volume,  then  neutralized  with  ammonia,  and 
treated  with  a  mixture  of  magnesium  sulphate  and  ammonium 
chloride,  it  gave  a  fine  crystalline  precipitate,  which  when  further 
examined  was  found  to  represent  very  nearly  the  fiftieth  of  a  grain 
of  phosphorus. 

Method  of  lApowitz. — If  in  the  application  of  this  method  the 
suspected  mixture,  after  the  addition  of  the,  fragments  of  sulphur, 
be  boiled  in  a  retort  with  a  long  neck,  or  the  latter  be  connected  with 
the  receiver  by  means  of  a  glass  tube,  and  the  operation  performed 
in  the  dark,  the  vapors  as  they  pass  through  the  tube,  if  they  contain 
phosphorus,  will  be  phosphorescent,  even,  as  we  have  in  several  in- 
stances found,  when  only  a  very  small  quantity  of  the  poison  is 
present.  In  this  manner  this  process  may,  as  it  were,  be  combined 
with  that  of  Mitscherlich.  Yet,  as  the  poison  would  thus  be  divided, 
part  of  it  remaining  in  the  retort  with  the  sulphur  and  part  passing 
over  into  the  receiver,  this  method  is  advisable  only  in  the  absence 
of  facilities  for  the  application  of  Mitscherlich's  method,  in  which 
the  whole  of  the  poison  may  be  collected  in  the  distillate. 

Dusart's  Method. — For  the  recovery  of  phosphorus  from  the  con- 
tents of  the  stomach,  intestines,  and  similar  mixtures,  the  following 
method  has  been  advised  by  L.  Dusart.  {Jour.  Chim.  Med.,  Sept. 
1874,  400.)  The  mass,  placed  in  a  flask,  is  treated  with  a  mixture 
of  equal  volumes  of  disulphide  of  carbon,  ether,  and  alcohol  in  which 
has  been  previously  dissolved  one-half  per  cent,  of  sulphur,  the 
ethereal  mixture  being  added  in  sufficient  quantity  to  form  when 
well  agitated  an  emulsion.  In  this  operation  any  free  phosphorus 
present  will  be  dissolved  by  the  disulphide  of  carbon  mixture,  and, 
uniting  with  the  dissolved  sulphur,  form  a  compound  of  phosphorus 
and  sulphur,  much  less  readily  oxidized  than  free  phosphorus. 

After  standing  twenty-four  hours,  the  ethereal  mixture  is  decanted, 
and  the  residue  extracted  a  second  and  third  time  in  the  same  manner. 
The  mixed  ethereal  liquids  are  quickly  filtered,  in  a  covered  funnel, 
into  a  retort,  and  then  metallic  copper  recently  reduced  by  hydrogen 
added  portions  at  a  time,  until  the  last  portions  remain  bright  after 


SKPA  RATION    FROM    ORGANIC    MIXTURES.  215 

warniin(r  the  niixtiirc  some  minutes.  After  some  hours,  the  mixture 
is  heated  on  a  water-bath  until  the  ethereal  liquid  has  distilled  over; 
there  will  then  remain  in  the  retort  a  little  water,  fatty  and  extrac- 
tive matters,  and  the  copper  covered  with  phosphorus  and  sulphur. 

The  coated  copper  is  collected  on  a  filter,  washed  with  alcohol, 
then  with  ether;  this  process  removes  the  fat,  and  leaves  the  copper 
compound  as  a  black  and  brilliant  substance,  which  is  not  sensibly 
acted  upon  by  the  air:  it  may  be  preserved  in  a  dark  flask  for  future 
examination.  To  show  the  presence  of  the  phosphorus  in  the  copj)er 
compound,  the  latter  is  placed  in  an  apparatus  in  which  pure  hydro- 
gen is  being  evolved  and  provided  with  a  tube  containing  a  caustic 
alkali,  as  heretofore  described,  when  phosphoretted  hydrogen  will  be 
evolved  and  burn  with  its  characteristic  green  color. 

Recovery  as  an  Oxide  of  Phosphorus. — If  the  phosphorus  has 
undergone  oxidation,  the  method  of  Mitscherlich,  as  already  stated, 
will  fail  to  reveal  its  presence.  But,  if  the  poison  has  only  passed 
to  the  state  of  phosphorous  acid,  it  may  still  be  detected  by  the  hydro- 
gen method,  either  directly  by  the  flame  reaction  or  after  conversion 
into  silver  phosphide  {ante,  205).  Should  it,  however,  have  passed 
to  the  state  of  phosphoric  acid,  then  this  method  will  also  fail. 

Under  these  circumstances,  the  mixture,  after  the  addition  of 
water,  and  filtration  if  necessary,  is  treated  with  a  few  drops  of  nitric 
acid  and  concentrated  to  a  small  volume.  It  is  then  treated  with 
slight  excess  of  pure  sodium  carbonate,  evaporated  to  dryness,  and 
the  residue  slowly  heated  to  fusion,  by  M-hich  the  organic  matter  will 
be  destroyed,  while  any  phosphoric  acid  present  will  remain  as  sodium 
phosphate.  The  residue  is  then  dissolved  in  a  small  quantity  of 
water,  and  the  solution  examined  by  the  usual  tests  for  phosphoric 
acid.  If,  however,  only  a  minute  quantity  of  phosphoric  acid  be 
thus  detected,  this  in  itself  will  be  no  evidence  that  the  phosphorus 
originally  existed  in  its  unoxidized  state,  since  that  acid  in  minute 
quantity  is  normally  present  in  most  organic  mixtures. 

Failure  to  detect  the  Poisox.— In  fatal  poisoning  by  phos- 
phorus, as  by  most  other  substances,  the  whole  of  it  may  be  eliminated 
from  the  body  previous  to  death,  even  when  death  takes  place  with 
the  usual  rapidity.  Then,  again,  as  this  substance  readily  undergoes 
oxidation,  it  may  thus,  at  least  as  free  phosphorus,  speedily  disap- 
pear from  the  dead  body.  In  Dr.  Lewinsky's  case,  already  cited,  in 
which  death  occurred  on  the  sixth  day,  a  chemical  examination  of 


216  PHOSPHORUS. 

the  stomach  and  its  contents,  by  Dr.  Schauenstein,  failed  to  yield 
any  indication  of  the  presence  of  phosphorus.  So,  also,  in  a  case 
reported  by  Dr.  Nitsche,  in  which  a  soldier  purposely  swallowed  the 
ends  of  six  ordinary  packets  of  phosphorus-matches  and  died  on  the 
fourth  day,  a  chemical  examination  of  the  stomach  and  a  portion  of  the 
intestines,  with  their  contents,  two  days  after  death,  revealed  no  evi- 
dence of  the  presence  of  the  poison.  [Amer.  Jour.  Med.  Sci.,  Jan. 
1858,  288.)  Early  in  the  history  of  this  case  a  large  quantity  of 
the  phosphorus  mixture  was  expelled  from  the  stomach  by  vomiting. 

Cases  are  reported,  however,  in  which  this  poison  was  detected 
after  comparatively  long  periods.  Thus,  in  a  case  quoted  by  Whar- 
ton and  Stills,  it  was  detected  in  the  contents  of  the  intestines  on  the 
tenth  day  after  it  had  been  taken.  And  in  a  case  reported  by  Dr. 
Ludwig,  in  which  a  child,  three  years  and  a  half  old,  was  poisoned 
by  phosphorus-paste,  about  one  grain  of  phosphorus  in  substance  was 
obtained  from  the  contents  of  the  stomach  and  intestines,  although 
the  body  had  been  buried  three  weeJcs.  (Jour,  de  Chim.  Med.,  1863, 
584.)  This  is  the  longest  period  we  find  recorded  after  which  the 
poison  has  yet  been  detected  in  its  free  state  in  the  human  subject. 

In  some  experiments  upon  guinea-pigs,  each  poisoned  with 
twenty-three  milligrammes  (about  one-third  grain)  of  phosphorus, 
MM.  Fischer  and  Miiller  [Zeits.  Anal.  Chem.,  1876,  57)  found  free 
phosphorus  in  the  body  at  the  end  of  eight  weeks;  in  twelve  weeks 
no  free  phosphorus,  but  phosphorous  acid ;  and  at  the  end  of  fifteen 
weeks  only  phosphoric  acid. 

Quantitative  Analysis. — Any  phosphorus  found  in  its  solid 
state,  or  obtained  by  Mitscherlich's  method,  may,  of  course,  be 
weighed  as  such'.  When,  however,  the  phosphorus  has  been  con- 
verted into  phosphoric  acid,  it  may  be  determined  as  magnesium 
pyrophosphate,  Mg2P207.  For  this  purpose  the  solution  is  treated 
with  slight  excess  of  a  clear  mixture  of  magnesium  sulphate,  ammo- 
nium chloride,  and  ammonia,  ai]d  allowed  to  stand  for  several  hours, 
in  order  that  the  precipitate  may  completely  separate.  The  precipi- 
tate is  then  collected  upon  a  filter,  washed  with  water  containing  a 
little  ammonia,  dried,  ignited,  and,  after  cooling,  weighed.  Every 
one  hundred  parts  of  the  ignited  residue,  if  pure,  correspond  to 
sixty-four  parts  of  phosphoric  oxide,  PgOg,  or  twenty-eight  parts  of 
free  phosphorus. 


ANTIMONY.  217 


CHAPTER   IT. 

ANTIMONY. 

History. — Antimony  is  a  bluish-white,  hard,  brittle  metal,  having 
a  density  of  about  6.7  :  its  symbol  is  Sb,  and  its  atomic  weight  122. 
Wlien  heated  to  near  redness,  it  takes  fire  and  burns  with  the  evolu- 
tion of  dense  white  fumes  of  sesquioxide  of  antimony.  The  metal 
is  unacted  upon  by  cold  sulphuric  acid,  but  the  hot  acid  converts  it 
into  an  oxide  with  the  evolution  of  sulphurous  oxide  gas.  Hot  con- 
centrated nitric  acid  oxidizes  it  chiefly  into  antimonic  acid  ;  hvfh'o- 
chloric  acid,  even  at  the  boiling  temperature,  has  little  action  u])on 
it,  but  it  is  readily  soluble  in  nitro-muriatic  acid. 

Antimony  forms  two  principal  oxides:  trioxide,  or  sesquioxide  of 
antimony,  known  also  as  antimonious  oxide,  Sb203,'and  pentoxide,  or 
antimonic  oxide,  SbgOg ;  the  first  of  these  oxides  is  basic,  the  other 
acid,  in  properties.  With  sulphur  the  metal  forms  two  sulphides, 
corresponding  in  composition  with  the  oxides  named.  Antimony 
also  unites  in  two  proportions  with  chlorine,  forming  trichloride,  or 
antimonious  chloride,  SbCls,  and  pentichloride,  or  antimonic  chloride, 
SbCl^. 

When  taken  in  its  pure  state  into  the  system,  antimony  seems  to 
be  inert.  But  several  of  its  preparations  are  more  or  less  poisonous. 
The  only  one  of  these,  however,  likely  to  become  the  subject  of  a 
medico-legal  investigation  is  tartar  emetic. 

Tartar  Emetic. 

Composition. — This  substance,  known  also  as  tartarized  antimony 
or  tartrate  of  antimony  and  potassium,  is  a  compound  of  potassium, 
oxide  of  antimony,  and  tartaric  acid,  with  water  of  crystallization,  its 
formula  being  2KSbOC4Hp^;  H.O;  molecular  weight  668.  It  is 
prepared  by  the  action  of  antimonious  oxide  upon  the  acid  tartrate 


218  AXTIMOXY. 

of  potassium,  or  cream  of  tartar;  thus:  2KHC4H^06 -rSb203  = 
2KSbOCiH40g ;  HoO.  Antimonious  oxide,  in  its  free  state,  is  a 
white  crystallizable  substance,  which  is  insoh;ble  in  water,  and  only 
sparingly  soluble  in  nitric  acid,  but  readily  soluble  in  hydrochloric 
and  tartaric  acids,  and  in  the  caustic  alkalies.  The  poisonous  effects 
of  tartar  emetic  are  entirely  due  to  the  presence  of  the  antimonious 
oxide. 

Symptoms. — As  a  summary  of  the  symptoms  usually  produced 
bv  tartar  emetic,  when  swallowed  in  large  quantity,  may  be  men- 
tioned the  following :  nausea,  violent  and  continuous  vomiting,  burn- 
ing pain  in  the  stomach  and  bowels,  profuse  purging,  great  thirst, 
violent  cramps,  small  and  feeble  pulse,  coldness  of  the  extremities, 
great  prostration,  and  in  some  instances  convulsions  and  delirium. 
The  matters  discharged  from  the  bowels  are  usually  very  fluid,  and 
frequently  contain  bile.  The  urine  is  generally  increased  in  quantity, 
and  its  passage  sometimes  attended  with  pain.  It  is  a  remarkable 
fact  that  in  several  of  the  reported  instances  of  poisoning  by  this 
substance  there  was  neither  vomiting  nor  purging ;  in  these,  how- 
ever, the  other  symptoms  were  present  in  an  aggravated  form. 

A  man  of  strong  constitution,  aged  fifty  years,  for  the  purpose  of 
self-destruction,  swallowed  about  thirty-seven  grains  of  tartar  emetic. 
Violent  vomiting,  excessive  purging,  and  convulsions  soon  ensued. 
On  the  morning  of  the  third  day,  he  complained  of  violent  pain 
in  the  epigastrium,  which  was  much  distended ;  he  spoke  with  diffi- 
culty, and  appeared  as  if  intoxicated ;  the  pulse  was  imperceptible. 
During  the  day  the  bowels  became  tympanitic  and  more  painful, 
and  delirium  supervened.  The  next  morning  all  the  symptoms 
were  aggravated,  and  in  the  evening  the  delirium  became  furious; 
convulsions  then  set  in,  and  death  occurred  during  the  night,  nearly 
four  days  after  the  poison  had  been  taken.  {Orfila's  Toxicologie, 
1852,  i."623.) 

The  following  remarkable  case  of  recovery  is  reported  by  Dr. 
J.  T.  Gleaves.  {Western  Jour,  of  3Ied.  and  Surg.,  Jan.  1848,  23.) 
A  young  man  of  strong  constitution  swallowed  a  tablespoonful  of 
tartar  emetic  (about  an  ounce).  In  an  hour  and  a  half  afterward, 
although  he  drank  freely  of  warm  water  and  repeatedly  tickled  his 
fauces  with  his  finger,  no  vomiting  had  occurred.  During  the  first 
three  hours  he  vomited  only  two  or  three  times,  and  the  matter 
ejected  was  chiefly  the  warm  water  taken  to  induce  vomiting.     Two 


IM'.ltlOl)    WHEN    FATAL.  219 

hours  alter  taking-  tlie  poison  there  was  vioh'iit  involuntary  |)iM-j;inj;, 
and  he  became  pulseless,  speechless,  and  was  apparently  <lyinf^.  Three 
hours  alter  the  oecuirrence,  when  the  case  was  first  H^T.n  hy  Dr.  Gleaves, 
the  breathing  was  slow  and  difficult,  the  lace  pale,  features  shrunken, 
eves  fixed,  {)upils  dilated,  and  the  surface  cold ;  there  was  no  pulse, 
and  the  patient  was  apparently  unconscious.  In  seven  hours  the 
purging  ceased,  consciousness  returned,  and  there  was  great  thirst, 
and  a  sense  of  burning  })ain  in  the  throat,  oesophagus,  stomach,  and 
bowels.  Great  irritability  of  the  stomach  ensued,  and  the  matters 
vomited  were  tinged  with  blood.  On  the  evening  of  the  following 
day,  the  patient  was  again  pulseless  and  speechless,  and  the  abdomen 
was  tympanitic  and  painful  to  the  touch.  The  vomiting  continued, 
but  the  purging  was  arrested.  On  the  third  day,  there  was  occasional 
vomiting,  and  the  throat  was  sore  and  covered  with  pustules;  there 
was  also  painful  micturition,  the  urine  being  copious  and  highly 
colored.  On  the  fourth  day,  the  whole  body  was  covered  with 
genuine  tartar  emetic  pustules.  After  a  few  days  these  began  to 
heal,  and  in  about  two  weeks  the  patient  was  perfectly  well. 

Fei'iod  when  Fatal. — A  child,  recovering  from  measles,  died  in 
an  hour  from  the  depressing  effects  of  three-quarters  of  a  grain  of 
tartar  emetic,  prescribed  as  a  medicine.  [Jour,  de  Chim.,  1847,  472.) 
In  a  case  reported  by  Dr.  C.  Ellis,  an  unknown  quantity  of  the 
poison  proved  fatal  to  a  young  lady,  aged  twenty-one  years,  in  seven 
hours.  The  symptoms  were  violent  vomiting  and  purging,  accom- 
panied with  a  sense  of  burning  in  the  mouth,  dryness  of  the  throat, 
and  great  thirst.  Death  took  place  apparently  from  exhaustion, 
without  convulsions  or  any  cerebral  symptoms.  {Boston  3Ied.  and 
Surg.  Jour.,  Dec.  1856,  400.)  In  a  case  reported  by  Dr.  Pollock, 
in  which  sixty  grains  of  tartar  emetic  had  been  taken,  death  occurred 
in  ten  hours.  {London  Med.  Gaz.,  May,  1850,  801.)  In  this  instance, 
the  patient,  a  robust,  healthy  man,  aged  about  thirty  years,  was  very 
soon  seized  with  violent  vomiting  and  retching.  In  two  hours  after 
the  poison  had  been  taken,  there  was  still  violent  retching  at  short 
intervals,  and  the  man  complained  of  heat  and  constriction  in  the 
throat,  and  pain  in  the  ei)igastrium ;  the  respiration  was  frequent ; 
the  skin  covered  wMth  perspiration  ;  the  pulse  rapid  and  small.  In 
a  few  hours  afterward  the  vomiting  ceased,  and  the  patient  became 
insensible ;  the  respiration  was  slow^  and  labored,  but  not  stertorous ; 
pulse  very  rapid  and  almost  imperceptible ;  and  the  power  of  swal- 


220  ANTIMONY. 

lowing  had  ceased.  Death  took  place  tranquilly,  and  without  con- 
vulsions. 

The  cases  now  cited  are  among  the  most  rapidly  fatal  yet  reported. 
Instances  are  recorded  in  which  death  did  not  occur  until  after  the 
lapse  of  several  days ;  and  Dr.  Deutseh  relates  a  case  in  which  a 
woman,  who  took  by  mistake  a  scruple  of  tartar  emetic,  was  brought 
exceedingly  low  by  its  violent  action,  and  died  in  the  course  of  a 
year  in  consequence  of  its  irritant  effects  upon  the  intestinal  canal. 
(Wharton  and  Stille,  Med.  Jur.,  553.) 

Fatal  Quantity. — Several  instances  are  on  record  in  which  very 
small  doses  of  tartar  emetic  produced  most  violent  symptoms. 
Thus,  in  an  instance  related  by  Dr.  A.  Stills  (3Iat.  Med.,  ii.  346),  a 
dose  of  not  more  than  half  a  grain  produced  violent  vomiting  and 
purging,  and  a  state  closely  resembling  the  collapse  of  cholera.  The 
patient  was  an  insane  female,  whose  general  health,  however,  was 
perfect.  Of  thirty-seven  cases  of  acute  poisoning  by  tartar  emetic 
collected  by  Dr.  Taylor,  sixteen  proved  fatal.  Of  the  fatal  cases, 
the  smallest  dose  was  in  a  child,  three-quarters  of  a  grain,  and  in  an 
adult,  two  grains ;  but  in  the  latter  case  there  were  circumstances 
which  favored  the  fatal  operation  of  the  poison.  (Gruy's  Hosp.  Rep., 
1857,  415.)  Mr.  Hartley  relates  two  instances  in  which  ten  grains 
each  proved  fatal  to  two  children,  aged  three  and  five  years  respec- 
tively. In  a  case  related  by  Dr.  C.  A.  Lee,  a  child  a  few  weeks  old, 
who  swallowed  about  fifteen  grains  of  the  salt  in  solution,  was  seized 
with  violent  vomiting  and  purging,  attended  with  convulsions,  which 
soon  proved  fatal.  {New  York  Med.  and  Phys.  Jour.,  xxx.  302.)  Two 
eases  have  already  been  cited  in  which  thirty-seven  grains  and  sixty 
grains  respectively  proved  fatal  to  healthy  adults. 

The  following  remarkable  case  of  recovery  is  related  by  Dr. 
McCreery.  A  physician  swallowed  half  an  ounce  of  tartar  emetic, 
put  up  by  mistake  for  Rochelle  salt.  In  about  thirty-five  or  forty 
minutes  after  taking  the  poison  he  experienced  some  nausea,  which 
in  about  five  minutes  more  was  succeeded  by  vomiting.  Copious 
draughts  of  green  tea  and  large  doses  of  tannin  were  then  adminis- 
tered ;  and  these  were  followed  by  the  exhibition  of  albumen  and  an 
infusion  of  flaxseed.  But  the  vomiting,  which  was  very  distressing, 
continued,  with  little  intermission,  for  several  hours.  There  was  also 
very  severe  purging,  with  most  violent  cramps  of  the  legs,  and 
slighter  ones  of  the  wrists.     The  first  evacuation  from  the  bowels 


I'O.ST-MOIiTKM    A  I'l'KA  UA  NCES.  2'2  1 

wjis  purely  serous;  those  which  lollovved  were  of  a  bilious  characttM-, 
but  very  loose:  there  were  no  erainps  of  the  stomach.  These  svimj>- 
toms  giadiKiily  subsided,  and  after  several  days  the  patient  was  (juite 
well.  (Ainer.  Jour.  Med.  >Sei.,  Jan.  1853,  131.)  In  a  ease  eoinniu- 
nicatcd  to  me  by  Dr.  R.  Denig,  a  woman  re<;overed  in  a  few  days 
after  taking  fully  sixty  grains  of  the  salt  in  solution.  Within  ten 
minutes  after  taking  the  dose  the  i)atient  experienced  great  distress 
and  burning  pain  in  the  stomach,  accompanied  by  retching  and 
vomiting.  A  case  is  recently  reported  in  which  recovery  took  place 
after  one  hundred  and  seventy  grains  of  the  salt  had  been  taken. 
(Med.  Rec,  New  York,  1883,  401.)  It  is  well  known  that  in  certain 
inflammatory  diseases  tartar  emetic  may  be  administered  in  very 
large  doses  without  producing  any  of  its  ordinary  effects. 

Treatment. — If  there  is  not  alreadv  free  vomiting;,  it  should 
be  promoted  by  the  administration  of  large  draughts  of  warm  water; 
or  the  stomach  may  be  emptied  by  means  of  the  stomach-pump. 
As  a  chemical  antidote,  various  vegetable  astringents,  such  as  a 
strong  infusion  of  Peruvian  bark,  green  tea,  nut-galls,  or  oak  bark, 
have  been  highly  recommended;  and  instances  are  reported  in  which 
their  exhibition  was  apparently  attended  with  very  great  advantage. 
It  has,  however,  been  denied  that  these  substances  serve  to  neutralize 
the  poison. 

After  the  poison  has  been  expelled  from  the  stomach,  opium  may 
be  administered  to  check  the  excessive  vomiting.  For  this  purpose 
a  strong  decoction  of  coffee  has  also  been  highly  recommended. 

Post-mortem  Appeaeanges. — In  the  case  cited  from  Orfila, 
which  proved  fatal  in  about  four  days,  the  mucous  membrane  of  the 
stomach,  except  near  the  gullet,  where  it  was  healthy,  was  red, 
tumefied,  and  covered  with  a  viscid  coating,  which  was  easily  sepa- 
rated ;  the  duodenum  Avas  in  a  similar  condition,  but  the  other 
intestines  were  healthy.  The  intestines  were  entirely  empty.  The 
brain  was  congested  and  softened.  The  organs  of  the  chest  were 
healthy. 

In  the  case  related  by  Dr.  Lee,  in  which  fifteen  grains  of  the 
poison  had  been  taken,  the  mucous  membrane  of  the  stomach  was 
red  and  softened,  and  on  holding  it  up  to  the  light  it  appeared  of  a 
bright  crimson  color.  The  stomach  contained  a  small  quautitv  of 
slimy  mucus,  and,  like  the  mucous  membrane,  Avas  softened.  The 
texture  of  the  cardiac  orifice  seemed  more  changed  than  that  of  the 


222  AXTIMONY. 

pyloric.  The  duodenum  was  of  a  deep  brown  color,  almost  livid, 
and  contained  the  same  kind  of  substance  as  found  in  the  stomach. 
The  inflammation  extended  no  farther  than  the  colon.  The  vessels 
of  the  scalp,  as  well  as  those  of  the  brain,  and  the  right  side  of  the 
heart,  were  distended  with  blood.  The  ventricles  of  the  brain  were 
half  filled  with  fluid,  and  there  was  effusion  between  the  pia  mater 
and  the  arachnoid  membranes. 

In  Dr.  Ellis's  case,  thirty-nine  hours  after  death,  the  body  was 
quite  rigid,  and  there  was  considerable  bluish  discoloration  about  the 
back  of  the  neck  and  the  hands.  The  stomach  contained  a  quantity 
of  gruel-like,  acid  liquid,  in  which  a  considerable  quantity  of  anti- 
mony was  found.  No  well-marked  morbid  appearances  were  detected 
in  any  of  the  abdominal  organs.     The  brain  was  not  examined. 

Chemical  Properties. 

General  Chemical  Nature. — Tartar  emetic,  as  found  in  the 
shops,  is  usually  in  the  form  of  a  white  amorphous  powder.  In  its 
pure  state  it  crystallizes  in  large,  transparent,  odorless  octahedrons 
having  a  rhombic  base.  The  crystals  are  slightly  efflorescent  at  or- 
dinary temperatures,  and  when  heated  to  100°  C.  (212°  F.)  become 
anhydrous. 

When  heated  in  a  reduction-tube,  by  the  flame  of  a  spirit-lamp, 
tartar  emetic  readily  blackens,  from  the  decomposition  of  the  organic 
acid,  and  is  soon  reduced  to  a  mixture  of  charcoal  and  metallic  anti- 
mony. It  undergoes  a  similar  change  when  heated  upon  platinum- 
foil,  quickly  destroying  the  platinum  in  contact  with  the  heated  mass. 
Heated  on  charcoal  before  the  blow-pipe  flame,  the  charred  mass 
burns  with  the  production  of  a  widely  diffused  incrustation,  the 
thicker  portions  of  which  have  a  whitish  color,  while  the  thinner 
ones  have  a  bluish  appearance;  at  the  same  time  it  yields  globules 
of  metallic  antimony,  which  boil  and  are  slowly  dissipated  by  the 
continued  action  of  the  het^t.  If  the  globules  are  allowed  to  cool^ 
they  will  be  found  exceedingly  brittle. 

According  to  R.  Brandes,  tartarized  antimony  is  soluble  in  from 
twelve  to  fourteen  parts  of  water  at  the  ordinary  temperature,  and 
in  less  than  three  parts  of  boiling  water.  From  a  warm  saturated 
solution  the  salt  separates  on  cooling  in  beautiful  bold  crystals, 
Plate  IV.,  fig.  4.  The  same  crystals  separate  when  one  grain  of  a 
1-lOOOth   or  stronger  solution  of\the  salt  is  allowed  to  evaporate 


\ 
\ 

\ 


SULPHURETTED    lIYDR(XiEN    TEST.  223 

spontaneously  to  dryness ;  from  more  dilute  solutions  the  residue  is 
usually  destitute  ot"  any  well-deiined  crystals.  Aqueous  solutions  of 
tartar  emetic  are  colorless,  have  a  nauseous,  metallic  taste,  and  a  feeble 
acid  reaction,  even  when  the  liquid  contains  only  the  1-lOOOth  of  its 
weight  of  the  salt.  These  solutions  after  a  time  undergo  decomjxj- 
sition,  the  organic  acid  giving  rise  to  a  filamentous  growth  :  we  have 
found  tliis  formation  make  its  appearance,  after  several  days,  in  solu- 
tions containing  even  less  than  the  l-50,000th  of  their  weight  of  the 
antimony  compound. 

Tartar  emetic  is  insoluble  in  alcohol.  If  this  liquid  be  added  to 
an  aqueous  solution  of  tartar  emetic  containing  even  something  less 
than  the  1-lOOth  of  its  weight  of  the  salt,  the  latter  is  precipitated 
in  the  form  of  plumose  crystals  ;  sometimes,  however,  the  precipitate 
also  contains  octahedral  crystals. 

Special  Chemical  Properties. — When  tartar  emetic  in  its 
solid  state  is  moistened  with  a  solution  of  sulphide  of  ammonium  or 
of  sulphuretted  hydrogen,  it  immediately  acquires  an  orange-red  color, 
due  to  the  production  of  a  sulpliide  of  antimony.  This  reaction  is 
peculiar  to  antimony,  and  will  manifest  itself  with  the  least  visible 
quantity  of  the  salt.  Even  the  residue  left  on  evaporating  one  grain 
of  liquid  containing  only  the  1-1 0,000th  of  a  grain  of  the  pure  salt 
will  yield  a  very  satisfactory  coloration. 

In  the  following  investigations  in  regard  to  the  special  reactions 
of  reagents  with  solutions  of  tartar  emetic,  pure  aqueous  solutions  of 
the  salt  were  employed.  The  fractions  employed  indicate  rlie  amount 
of  sesqaioxide  of  antimony,  SbgO,,  present  in  one  grain  of  the  solution. 
The  amount  of  crystallized  tartar  emetic  represented  in  these  cases 
may  be  readily  obtained  by  multiplying  the  fractions  by  2.28. 

1.  Sulphuretted  Hydrogen. 

From  somewhat  strong  normal  solutions  of  tartar  emetic  this 
reagent  throws  down  a  deep  orange-red  precipitate  of  sesquisulphide 
of  antimony,  or  antimonious  sulphide,  Sb2S3 ;  in  more  dilute  solutions 
it  produces  an  orange-red  turbidity,  but  no  precipitate,  at  least  for 
several  hours.  The  formation  of  the  precipitate  from  dilute  solutions 
is  much  facilitated  by  heat.  From  solutions  acidulated  with  hydro- 
chloric acid,  however,  even  when  very  dilute,  the  reagent  produces  an 
immediate  precipitate. 

The  precipitate  is  insoluble   in   diluted   hydrochloric   acid,  but 


224  ANTIMONY. 

soluble  in  the  concentrated  acid,  even  at  ordinary  temperatures,  and 
still  more  readily  under  the  action  of  heat,  with  the  formation  of 
trichloride  of  antimony  and  the  evolution  of  sulphuretted  hydrogen 
gas.  Fuming  nitric  acid  converts  it  into  a  white  insoluble  compound 
of  antimony.  It  is  readily  soluble  in  the  fixed  caustic  alkalies,  but 
insoluble  in  ammonia :  at  least  we  find  that  when  one  part  of  the 
moist  precipitate  is  frequently  agitated  for  some  days  with  10,000 
parts  of  ammonia  solution  it  does  not  entirely  disappear,  and  that 
one  part  with  even  25,000  parts  of  ammonia  requires  some  hours  for 
solution.  When  dried  and  fused  with  sodium  nitrate,  it  gives  rise 
to  sodium  metantimoniate  and  sulphate. 

In  the  following  examination  in  regard  to  the  limit  of  this  test, 
Jive  grains  of  the  antimony  solution,  placed  in  a  small  test-tube,  were 
acidulated  with  hydrochloric  acid,  and  then  treated  with  the  reagent. 

1.  1-lOOth  solution  of  sesquioxide  of  antimony  (=^  grain  SbgOg) 

yields  a  very  copious,  light  orange-red  precipitate.  Solutions 
of  tartar  emetic  as  strong  as  this  require  about  half  their  vol- 
ume of  hydrochloric  acid  to  redissolve  the  precipitate  first  pro- 
duced by  the  acid.  When  tartaric  acid  is  employed  as  the  acidi- 
fying agent,  the  precipitate  produced  by  the  sulphur  reagent  has 
a  much  deeper  red  color  than  when  produced  in  the  presence, 
of  hydrochloric  acid. 

2.  1-lOOOth  solution  :   an  immediate  precipitate,  which  very  soon 

becomes  quite  abundant.  A  normal  solution  of  tartarized  anti- 
mony of  this  strength  yields  with  the  reagent  a  deep  orange 
solution,  but  no  precipitate,  even  after  standing  twenty-four 
hours. 

3.  1-1 0,000th  solution :  an  immediate  turbidity,  and,  after  a  little 

time,  a  good  deposit.  If  the  mixture  be  warmed,  the  precipitate 
sejjarates  almost  immediately.  When  the  solution  is  acidulated 
with  tartaric  acid,  the  precipitate  requires  several  hours  for  its 
separation, 

4.  l-25,000th  solution  :  in  a  very  little  time  the  mixture  acquires 

an  orange  tint ;  and  after  several  hours  there  is  a  satisfactory 
deposit. 

5.  l—50,000th  solution  :  in  a  little  time  the  liquid  assumes  a  yellow 

tint,  then  a  reddish  hue,  and  after  several  hours  yields  a  quite 
perceptible  orange-yellow  deposit. 

6.  l-100,000th  solution  :  after  some  minutes  the  liquid  acquires  a 


LEAD    AND    ZINC    TESTS,  225 

faint  yullow  tint,  hut  undergoes  no  further  change  for  at  Ica.'^t 
several  hours. 

The  reaction  of  this  reagent,  as  already  intimated,  is  quite  char- 
acteristic of  antimony.  If  the  precipitate  be  dissolved  in  hot  hydro- 
chloric acid,  and  the  solution  after  cooling  treated  with  several  times 
its  volume  of  water,  it  yields  a  white  precipitate,  consisting  of  ses- 
quioxide  and  trichloride  of  antimony,  which  after  a  time  becomes 
crystalline,  and  is  readily  soluble  in  tartaric  acid. 

Sulphide  of  Ammonium,  also,  throws  down  from  comparatively 
strong  normal  solutions  of  tartar  emetic  a  precipitate  of  sesquisul- 
phide  of  antimony,  which  is  soluble  in  excess  of  the  reagent.  In 
five  grains  of  a  1-lOOOth  solution  of  sesquioxide  of  antimony  the 
reagent  produces  a  good  yellow-orange  deposit.  In  more  dilute 
solutions  it  fails  to  produce  a  precipitate,  but  communicates  to  the 
liquid  an  orange  or  yellowish-red  color.  In  the  presence  of  a  free 
acid,  however,  it  precipitates  even  highly  dilute  solutions  of  the  salt. 

2.  Acetate  of  Lead. 

This  reagent  produces  in  normal  solutions  of  tartar  emetic  a  white 
amorphous  precipitate  of  the  double  tartrate  of  antimony  and  lead, 
.  Pb(SbO)2CsH80i2,  which  is  readily  soluble  in  acetic  and  tartaric  acids, 
and  decomposed  by  nitric  acid  with  the  production  pf  a  white  floccu- 
lent  deposit. 

1.  YW^  grain  of  sesquioxide  of  antimony,  as  tartar  emetic,  in  one 

grain  of  water,  yields  a  very  copious  precipitate. 

2.  Y^jj-jj  grain  :  a  very  good  flocculent  precipitate. 

3.  i-g-.Voir  grai"  yields  a  very  satisfactory  deposit. 

4.  2T,Voi7   grain :    after  a  little   time  the  mixture   becomes   quite 

turbid. 
Acetate  of  lead  also  produces  white  precipitates  in  solutions  of 
various  other  substances.  But  the  antimony  deposit  diflfers  from  all 
these  in  that  when  washed  and  moistened  with  sulphide  of  ammo- 
nium it  immediately  assumes  an  orange-red  color;  after  a  little 
time,  however,  this  color  changes  to  a  dark  brown  or  nearly  black 
hue. 

3.  Metallic  Zinc. 

When  a  drop  of  a  solution  of  tartar  emetic  is  placed  on  a  piece 
of  platinum-foil  and  acidulated  with  a  small  drop  of  hydrochloric 
acid,  the  addition  of  a  fragment  of  zinc  causes  the  separation  of 

15 


226  .  ANTIMONY. 

metallie  antimony,  which  adheres  to  the  platinum  covered  by  the 
liquid,  forming  a  black  or  brownish  stain  (Fresenius).  The  deposit 
is  readily  soluble  in  nitric  acid,  especially  if  warmed,  but  only 
sparingly  soluble  in  concentrated  hydrochloric  acid ;  when  washed 
and  dried,  it  is  easily  dissipated  by  heat. 

1.  YoT  gJ'ain  of  sesquioxide  of  antimony,  in  solution  in  one  grain  of 

water,  when  treated  in  the  above  manner,  yields  a  very  copious, 
deep  black  deposit. 

2.  YWU^  grain  :  a  very  good  deposit. 

3.  3  Q^Q  Q   grain :  after  a  very  little  time  there  is  a  very  satisfactory 

dark-brown  stain. 

4.  Yo'.Too"  g^^i"^  •  after  a  few  minutes  a  very  distinct  brownish  stain 

makes  its  appearance. 

The  antimonial  nature  of  these  deposits  may  be  shown  by  moist- 
ening the  washed  stain  with  nitric  acid,  and  evaporating  to  dryness 
at  a  gentle  heat,  when  the  residue,  on  being  touched  with  sulphide 
of  ammonium,  will  assume  an  orange-red  color. 

Under  the  action  of  this  test  solutions  of  arsenic  yield  no  de- 
posit ;  whilst  solutions  of  tin  yield  a  deposit  upon  the  zinc,  but  none 
upon  the  platinum. 

4.  Metallie  Copper. 

When  a  solution  of  tartar  emetic  is  acidulated  with  hydrochloric 
acid,  and  boiled  with  a  slip  of  bright  copper-foil,  the  antimony  com- 
pound undergoes  decomposition  with  the  deposition  of  metallio  anti- 
mony upon  the  copper,  in  the  form  of  a  violet  or  gray  coating,  the 
color  depending  upon  the  thickness  of  the  deposit.  It  is  obvious 
that  the  thickness  of  the  deposit  produced  by  a  given  quantity  of 
the  metal  will  depend  upon  the  size  of  the  copper-foil  employed  in 
the  experiment. 

When  one  grain  of  the  tartar  emetic  solution,  placed  in  a  thin 
watch-glass,  is  acidulated  and  heated  with  a  very  minute  portion  of 
the  foil,  it  yields  as  follows : 

1.  yl-g-  grain  of  sesquioxide  of  antimony:  the  copper  immediately 

assumes  a  violet  color,  and  soon   receives  a  thick,  dark-gray 
coating. 

2.  YiroT  gi'ain  yields  much  the  same  results  as  1. 

3.  Yir.Wo  gi*ain :  in  a  little   time  the  copper  presents  a  beautiful 

violet  color. 


HYDROGEN    TEST.  227 

4.  ^tj-.Vfc  S'"*'^'''  yields  u  very  distinet  reaction. 

5.  -nn/.TnriT  S'"''"  •   ^^'''en  the  liquid  is  evaporated  to  near  dryness,  the 

copjjer  acquires  a  perceptible  violet  tai-ui.sh. 

The  j)roduction  of  a  metallic  deposit  ui)on  copper  under  tlie 
aln)ve  conditions  is  common  to  antimony,  arsenic,  mercury,  and 
some  few  other  metals.  The  violet  color  of  the  antimony  deposit 
is  rather  peculiar;  hut  the  deposit  from  this  metal  does  not  always 
present  this  color,  and,  moreover,  very  thin  deposits  of  arsenic  may 
present  a  similar  hue.  When  the  coated  copper  is  washed,  dried, 
and  heated  in  a  narrow  reduction-tube,  the  antimony  deposit,  if  not 
in  too  minute  quantity,  yields  a  sublimate  which  forms  quite  near 
the  heated  slip  of  copper,  and  is  generally  amorphous,  or  at  most 
granular,  in  form,  but  it  may  contain  well-defined  octahedral  crystals 
of  antimonic  oxide,  and  sometimes  crystalline  needles.  The  arsenic 
deposit  under  like  conditions  is  vaporized  at  a  lower  temperature, 
and  yields,  under  proper  conditions,  a  sublimate  fully  half  an  inch 
above  the  copper,  and  consisting  wholly  of  octahedral  crystals.  The 
sublimate  from  mercury  appears  in  the  form  of  minute  metallic 
globules.  The  other  metals  referred  to  fail  to  yield  a  sublimate 
when  thus  treated. 

The  true  nature  of  the  antimony  deposit  may  be  shown,  as  first 
advised  by  Mr.  Watson,  by  boiling  the  coated  copper  in  a  dilute 
solution  of  caustic  potash,  the  coated  metal  being  occasionally  with- 
drawn from  the  liquid  and  exposed  to  the  air  to  favor  the  oxidation 
of  the  antimony,  when,  after  a  time,  the  deposit  will  be  entirely  dis- 
solved as  antimoniate  of  potassium.  On  now  removing  the  copper- 
foil,  and  acidulating  the  liquid  with  hydrochloric  acid,  concentrating 
to  a  small  volume,  and  then  treating  it  with  sulphuretted  hydrogen 
gas,  pentasulphide  of  antimony,  SbgSs,  of  an  orange-red  color,  will 
be  precipitated.  This  method  will  serve  to  identify  even  very  small 
deposits  of  the  metal. 

5.  Antimonuretted  Hydrogen. 

When  a  solution  of  tartar  emetic,  or  of  any  of  the  soluble  salts 
of  antimony,  is  mixed  with  zinc  and  sulphuric  acid,  in  the  propor- 
tion to  evolve  hydrogen,  the  salt  is  decomposed  and  the  antimony 
evolved  as  antimonuretted  hydrogen  gas,  SbHj.  This  decomposi- 
tion may  be  effected  in  the  apparatus  of  Marsh,  first  devised  for  the 
detection  of  arsenic.  Fig.  3. 


228 


ANTIMONY. 


Pure  zinc  and  sulphuric  acid,  previously  diluted  with  about  four 
volumes  of  water,  are  placed  in  the  flask  A,  which  is  furnished  with  a 
drying-tube,  c,  and  a  reduction-tube,  d,  the  latter  of  which  is  of  hard 
glass  and  made  to  terminate  in  a  drawn-out  point.  The  drying-tube 
should  be  loosely  filled  with  fragments  of  calcium  chloride.  When 
only  a  minute  quantity  of  antimony  solution  is  to  be  examined,  the 
glass  flask  may  be  replaced  by  a  test-tube.  After  the  apparatus  has 
become  completely  filled  with  hydrogen,  a  small  quantity  of  the  an- 

PlG.    3. 


Apparatus  for  the  detection  of  antimony . 


timony  solution  is  introduced  into  the  flask  by  means  of  the  funnel- 
tube  a,  when  in  a  few  moments  the  evolved  gas  will  contain  anti- 
monuretted  hydrogen,  the  presence  of  which  may  be  shown  by  three 
different  methods. 

1.  If  the  gas  as  it  escapes  from  the  end  of  the  reduction-tube 
be  ignited,  it  burns  with  a  bluish  flame,  and,  unless  the  amount 
of  antimony  present  is  very  minute,  evolves  white  fumes  of  sesqui- 
oxide  of  antimony.  If  these  fumes  be  received  upon  a  cold  surface, 
as  a  piece  of  porcelain,  they  yield  a  white  amorphous  deposit,  which 


irYDUOQEN    TEST.  229 

immediately  acquires  an  orange-red  color  when  moistened  with  sul- 
pliide  of  ammonium.  If  a  piece  of  cold  porcelain,  held  in  a  hori- 
zontal position,  be  brought  in  contact  with  the  flame,  the  antimony 
will  condense  in  the  form  of  a  black,  nearly  circular  spot  or  stain, 
which  is  usually  surrounded  by  a  grayish  ring;  as  soon  as  a  spot  has 
thus  formed,  the  Hame  should  be  received  upon  a  fresh  portion  of 
the  porcelain. 

If  the  experiment  be  performed  in  a  small  apparatus,  fifty  grains 
of  a  fluid  mixture  containing  the  l-10,000th  of  its  weight  of  sesqui- 
oxide  of  antimony  (=^J^  grain  Sb^)  will  yield  quite  a  number 
of  spots  of  the  metal. 

Antimony  and  arsenic  are  the  only  metals  that  under  the  above 
conditions  will  yield  metallic  spots  upon  a  cold  surface.  The  spots 
from  these  two  metals  generally  differ  somewhat  in  regard  to  theu- 
])hysical  appearance,  those  from  antimony  being  usually  dull,  whereas 
those  from  arsenic  have  generally  a  bright  metallic  lustre.  They 
differ  greatly,  however,  in  regard  to  some  of  their  other  properties. 
Thus,  the  antimony-stains  are  slowly  and  with  difficulty  dissipated 
by  the  flame  of  a  spirit-lamp,  whilst  those  from  arsenic  are  readily 
volatilized.  Again,  the  antimony  spots  readily  dissolve  in  yellow 
sulphide  of  ammonium,  and  the  solution,-  even  from  very  small  stains, 
when  gently  evaporated  to  dryness,  leaves  a  red  or  orange-red  residue 
of  sulphide  of  antimony,  which  is  soluble  in  strong  hydrochloric 
acid,  but  insoluble  in  ammonia;  whereas  the  arsenic-stains  dissolve 
but  slowly  in  yellow  sulphide  of  ammonium,  and  the  solution  leaves 
upon  evaporation  a  yellow  residue  of  arsenious  sulphide,  insoluble 
in  hydrochloric  acid,  but  readily  soluble  in  ammonia.  Moreover, 
the  antimony-stains  are  insoluble  or  dissolve  with  great  difficulty  in 
a  solution  of  sodium  or  calcium  hypochlorite,  whilst  the  arsenic  spots 
readily  disappear  when  touched  with  a  solution  of  this  kind. 

2.  When  a  portion  of  the  reduction-tube  is  heated  to  redness,  the 
antimonuretted  hydrogen  passing  through  the  tube  is  decomposed 
with  separation  of  metallic  antimony,  which,  when  only  in  small 
quantity,  is  deposited  within  the  tube  wholly  on  the  inner  side  of 
the  part  to  which  the  flame  is  directly  applied,  but  when  in  larger 
quantity,  on  both  sides  of  the  flame.  Arsenic  under  like  circum- 
stances yields  a  somewhat  similar  deposit;  but  in  this  case  tlie  whole 
of  the  metal  is  deposited  in  the  tube  on  the  outer  side  of  the  part  to 
which  the  flame  is  applied. 


230  ANTIMONY. 

A  much  smaller  quantity  of  antimony  will  in  this  manner  fur- 
nish a  deposit  that  will  produce  spots  from  the  ignited  jet  upon 
porcelain.  Fifty  grains  of  a  solution  containing  the  1-50, 000th  of 
its  weight  of  sesquioxide  of  antimony  (=  yfto  gi^ain  SbgOg),  when 
treated  in  a  small  apparatus,  will  yield  a  very  good  brownish-black 
deposit;  and  a  similar  quantity  of  a  l-500,000th  solution,  a  very 
distinct  brownish  stain,  within  the  heated  tube.  Deposits  of  the 
metal  produced  by  this  method  exhibit  the  same  chemical  reactions 
as  those  produced  on  porcelain  by  the  ignited  gas. 

3.  If  the  antimonuretted  hydrogen  be  conducted  into  a  solu- 
tion of  silver  nitrate,  the  whole  of  the  antimony  is  precipitated 
as  antimonide  of  silver,  AggSb,  in  the  form  of  a  black  powder. 
The  chemical  reaction  in  this  case  is  as  follows:  SbH3-l-3Ag]S[03  = 
AggSb  +  3HNO3.  When  only  a  minute  trace  of  antimony  is  pres- 
ent, the  whole  of  the  precipitate  collects  in  the  lower  end  of  the 
delivery-tube,  in  the  form  of  a  black  ring. 

This  reaction  is  extremely  delicate,  and  the  method  can  be  applied 
with  a  much  smaller  quantity  of  fluid  than  either  of  those  just  men- 
tioned. When  the  operation  is  performed  in  a  small  test-tube  and 
the  evolved  gas  conducted  into  a  few  drops  of  the  silver-solution, 
five  fluid-grains  of  a  1-1 0,000th  solution  of  the  antimony  oxide  will 
produce  a  quite  large,  black  deposit,  much  of  which  remains  in  the 
end  of  the  delivery-tube.  A  similar  quantity  of  a  l-50,000th 
solution  produces  after  several  minutes  a  very  satisfactory  deposit ; 
and  a  l-100,000th  solution  will  produce  in  about  fifteen  minutes  a 
very  distinct  reaction. 

Solutions  of  arsenic,  of  sulphides,  and  of  several  other  substances 
will  also  under  similar  conditions  evolve  gaseous  compounds,  which 
produce  black  precipitates  in  a  solution  of  silver  nitrate.  In  the 
action  of  the  arsenical  compound,  the  precipitate  consists  alone  of 
metallic  silver,  the  arsenic  being  oxidized  into  arsenious  oxide, 
which  remains  in  solution. 

The  true  nature  of  the  antimony  precipitate,  or  antimonide  of 
silver,  may  be  shown  by  collecting  the  deposit  on  a  filter,  washing 
with  warm  water,  and  boiling  with  dilute  hydrochloric  acid,  in  which 
the  antimony  will  dissolve,  while  the  silver  will  remain  in  an  in- 
soluble form.  If  the  quantity  of  precipitate  present  is  too  minute 
to  be  separated  from  the  filter,  the  portion  of  the  latter  containing 
the  deposit  is  boiled   in  the  dilute  hydrochloric  acid.     When  the 


CHEMICAL   PROPERTIES.  231 

acid  mixture  lias  cooled  and  llu;  deposit  completely  subsided,  it  is 
transferred  to  a  filter  wliicli  has  previously  been  moistened  with 
water,  and  the  filtration  repeated  if  necessary  until  the  filtrate  is 
perfectly  elear.  On  now  treating;  the  solution  with  sulphuretted 
hydrogen,  sesquisulphide  of  antimony,  of  its  peculiar  color,  will  he 
tiirown  down. 

Professor  ITofraann  has  recommended  to  boil  the  washed  anti- 
monide  of  silver  with  a  solution  of  tartaric  acid,  in  which  the 
antimony  readily  dissolves,  while  the  silver  remains  unchanged; 
the  solution  is  then  filtered  and  treated  with  sulphuretted  hydro- 
gen. {Quart.  Jour.  Chem.  Soc,  April,  1860,  79.)  By  either  of  the 
methods  now  considered,  an  exceedingly  minute  quantity  of  anti- 
mony may  be  recovered  from  the  silver  precipitate. 

From  what  has  already  been  stated,  it  is  obvious  that  the  method 
under  consideration  will  serve  to  detect  antimony  in  the  presence  of 
arsenic,  and  the  latter  in  the  presence  of  the  former.  And  this  may 
be  effected  even  when  the  metals  are  present  in  very  minute  and 
disproportionate  quantities. 

Antimonuretted  hydrogen  is  also  decomposed  by  an  alcoholic 
solution  of  potassium  hydrate,  with  the  production  of  a  black 
precipitate.  Arsenic  under  similar  conditions  fails  to  produce  a 
precipitate. 

Other  Reactions  of  Tartar  Emetic— A'iV/'fc  acid  produces 
in  somewhat  strong  solutions  of  tartar  emetic  a  white  amorphous 
precipitate,  which,  according  to  Geiger,  consists  of  a  basic  nitrate  of 
antimonic  oxide.  The  precipitate  is  soluble  only  in  very  large  excess 
of  the  acid,  but  is  readily  soluble  in  tartaric  acid ;  in  solutions  con- 
taining free  tartaric  acid,  therefore,  the  reagent  fails  to  produce  a 
precipitate.  When  the  washed  precipitate  is  touched  with  sulphide 
of  ammonium,  it  immediately  assumes  an  orange-red  color.  One 
grain  of  a  1-lOOth  solution  of  sesquioxide  of  antimony  when  treated 
with  a  drop  of  the  acid  yields  a  quite  copious  deposit,  which  does 
not  disappear  on  the  further  addition  of  several  drops  of  the  reagent. 
One  grain  of  a  1-1 00th  solution  yields  with  a  small  drop  of  the 
acid  a  very  fair  precipitate. 

Hydrochloric  acid  occasions  in  concentrated  solutions  of  the  salt 
a  white  precipitate,  which  is  much  more  readily  soluble  in  excess  of 
the  reagent  than   in  the  preceding  reaction;  it  is  also  very  readily 


232  ANTIMONY. 

soluble  in  tartaric  acid.  One  grain  of  a  1-lOOth  solution  of  sesqui- 
oxide  of  antimony  yields  with  a  drop  of  the  reagent  a  quite  good 
precipitate,  which  disappears  when  the  mixture  is  stirred.  This  acid 
also  produces  white  precipitates  in  solutions  of  silver,  of  lead,  and 
of  mercuroas  combinations.  The  silver  precipitate  is  readily  soluble 
in  ammonia,  and  that  from  mercury  is  turned  black,  whilst  the  pre- 
cipitates from  lead  and  antimony  are  unchanged  by  this  reagent. 
Sulphide  of  ammonium  causes  the  antimony  precipitate  to  assume 
an  orange-red  color,  whilst  it  turns  the  lead-deposit  black.  The 
antimony  precipitate  is  the  only  one  of  these  that  is  soluble  in  tar- 
taric acid. 

Sulphurie  acid  throws  down  from  similar  solutions  a  white  amor- 
phous precipitate,  which  becomes  orange-red  when  touched  with 
sulphide  of  ammonium.  The  production  of  a  white  precipitate  by 
this  acid  is  common  to  solutions  of  several  other  metals. 

Ammonia  precipitates  from  solutions  of  tartar  emetic  white 
sesquioxide  of  antimony,  which  is  insoluble  in  excess  of  the  pre- 
cipitant. One  grain  of  a  1-lOOth  solution  of  the  antimony  oxide 
yields  a  very  good  precipitate;  and  a  similar  quantity  of  a  1-1 000th 
solution  yields  a  quite  fair,  granular  deposit,  especially  if  the  mix- 
ture be  stirred.  Ammonium  carbonate  fails  to  produce  a  precipitate 
even  in  concentrated  solutions  of  the  antimonial  compound. 

Potassium  and  Sodium  hydrates  produce  in  quite  concentrated 
solutions  of  the  salt  white  amorphous  precipitates,  which  are  readily 
soluble  in  excess  of  either  reagent.  The  carbonates  of  these  alkalies, 
however,  throw  down  white  precipitates  that  are  insoluble  in  excess 
of  the  precipitant;  the  limit  of  these  reactions  is  about  the  same  as 
that  of  ammonia. 

When  a  solution  of  tartar  emetic  is  treated  with  sufficient  excess 
of  potassium  hydrate  to  redissolve  the  precipitate  first  produced,  and 
a  solution  of  silver  nitrate  then  added,  it  produces  a  brownish-black 
precipitate,  consisting  of  a  mixture  of  suboxide  and  monoxide  of 
silver,  while  the  antimony  remains  in  solution  as  potassium  anti- 
raoniate.  If  the  precipitate  thus  produced  be  treated  with  ammonia, 
the  monoxide  of  silver  is  dissolved,  while  the  suboxide  remains  as 
a  dense  black  powder.  One  grain  of  a  1-1 0,000th  solution  of  anti- 
mony sesquioxide,  when  treated  after  this  method,  will  yield  a  very 
satisfactory  black  deposit ;  and  the  reaction  is  visible  when  a  similar 
quantity  of  even  a  l-25,000th  solution  of  the  antimony  compound 


SEPARATION    FUOM    OROAXIC    MIXTURES.  '233 

is  tMiiployecl.     Nitrate  ol"  silver  alone   inoiliices   in   solutions  of  the 
antimony  salt  a  white  precipitate. 

Corrosive  sublimate  slowly  tiirows  clown  from  solutions  of  the 
salt,  even  when  quite  dilute,  a  white  floeculent  precipitate.  C'hro- 
mate  and  dichromatc  of  potassium  impart  to  very  strong  solutions 
a  greenish  color,  and  throw  down  a  slight,  greenish  precipitate. 
Ferro-  i\iu\  ferri-ci/a)ude  of  jjotassium  fail  to  produce  a  preci[)itate 
even  in  concentratetl  solutions  of  the  antimony  com})ound. 

Separation  from  Organic  Mixtures. 

Suspected  Solutions. — The  same  method  of  analysis  is  equally 
apjdicable  for  the  examination  of  suspected  articles  of  food  or  drink, 
vomited  matters,  aud  the  contents  of  the  stomach.  The  mixture, 
after  the  addition  of  water  if  necessary,  is  acidulated  with  hydro- 
chloric acid,  a  little  tartaric  acid  added,  and  the  whole  exposed  to  a 
gentle  heat  for  about  fifteen  minutes.  When  the  mixture  has  cooled, 
it  is  thrown  upon  a  muslin  strainer,  the  strained  liquid  filtered,  and 
the  filtrate,  after  concentration  if  necessary,  exposed  to  a  current  of 
sulphuretted  hydrogen  gas  as  long  as  a  precipitate  is  produced,  and 
then  allowed  to  stand  in  a  moderately  warm  place  for  several  hours, 
in  order  that  the  precipitate  may  completely  subside. 

If  antimony  is  present  in  comparatively  large  quantity,  the  pre- 
cipitate thus  obtained  will  have  a  more  or  less  orange-red  color ;  if, 
however,  the  metal  is  present  in  only  minute  quantity,  or  the  deposit 
contains  much  organic  matter,  it  will  present  a  yellow  or  brownish 
appearance.  The  precipitate  is  now  collected  upon  a  filter,  washed 
with  water  containing  a  little  hydrochloric  acid,  and  then  heated  with 
strong  hydrochloric  acid,  when  any  sesquisulphide  of  antimony  present 
will  be  decomposed  and  the  metal  dissolved  as  trichloride.  After 
solution  has  taken  place,  the  heat  should  be  continued  until  the  odor 
of  the  sulphuretted  hydrogen,  evolved  by  the  decomposition,  has 
entirely  disappeared. 

A  small  portion  of  the  clear  liquid  may  now  be  examined  by  the 
zinc  and  copper  tests  in  the  manner  already  described,  except  that  it 
is  not  necessary  to  add  hydrochloric  acid,  since  this  is  already  present. 
Another  portion  of  the  liquid  may  be  treated  with  large  excess  of 
water,  when  the  antimony,  unless  present  in  only  very  minute  quan- 
tity, will  be  precipitated  as  white  oxychloride  (5Sb203 ;  2SbCl3),  the 


234  ANTIMONY. 

true  nature  of  which  is  fully  established  by  its  assuming  an  orange- 
red  color  when  moistened  with  sulphide  of  ammonium,  as  well  as 
by  its  ready  solubility  in  tartaric  acid.  Should  these  tests  yield  posi- 
tive reactions,  a  given  portion  of  the  solution,  properly  diluted,  may 
be  treated  with  sulphuretted  hydrogen  gas,  and  from  the  amount 
of  antimony  sesquisulphide  obtained,  the  quantity  of  tartar  emetic 
determined  in  the  manner  hereafter  described. 

If  it  is  desired  to  reconvert  the  antimony  present  in  the  hydro- 
chloric acid  solution  into  tartar  emetic,  it  may  be  precipitated,  by 
addition  of  water,  as  oxychloride,  and  the  precipitate  collected, 
washed,  and  then  agitated  for  some  time  with  a  very  dilute  solution 
of  sodium  carbonate.  In  this  operation  the  oxychloride  of  anti- 
mony will  be  entirely  converted  into  sesquioxide  of  the  metal,  the 
chlorine  being  taken  up  as  chloride  of  sodium  :  care  should  be  taken 
to  employ  only  a  very  dilute  solution  of  the  sodium  salt,  since  other- 
wise more  or  less  of  the  antimorly  compound  might  be  dissolved. 
The  precipitate  is  now  collected,  washed,  and  digested  at  a  moderate 
heat  with  a  little  water  containing  an  appropriate  quantity  of  potas- 
sium tartrate,  or  cream  of  tartar,  when  it  will  be  dissolved  as  tartar 
emetic,  the  presence  of  which  may  be  determined  by  the  usual  tests. 

Should  the  precipitate  produced  from  the  original  solution  by 
sulphuretted  hydrogen  have  a  dark  color,  it  should  not  be  con- 
cluded, from  this  circumstance  alone,  that  the  metal  is  entirely 
absent;  since  it  might  be  present  even  in  very  notable  quantity, 
and  yet  the  peculiar  color  of  its  sulphide  be  entirely  masked  by  the 
presence  of  organic  matter. 

Under  these  circumstances,  the  washed  precipitate,  placed  in  a 
thin  porcelain  dish,  may  be  treated  with  a  few  drops  of  concentrated 
nitric  acid,  and  the  mixture  cautiously  evaporated  to  dryness,  the 
operation  being  repeated,  if  necessary,  until  the  organic  matter  is  well 
destroyed.  Any  antimony  present  will  now  exist  as  an  oxide  of  the 
metal.  The  residue  is  then  moistened  with  a  few  drops  of  a  strong 
solution  of  potassium  hydrate,  the  liquid  expelled  by  a  moderate 
heat,  and  the  dry  residue  very  gradually  heated  to  fusion.  The 
cooled  mass  is  stirred  with  a  little  water,  the  mixture  acidulated 
with  tartaric  acid,  then  boiled  for  some  minutes,  and  the  solution 
filtered.  The  whole  of  the  antimony  will  now  be  present  in  the 
filtrate,  which,  if  the  operations  have  been  conducted  with  care, 
will  be  perfectly  colorless.     A  portion  or  the  whole  of  the  solu- 


SEPARATION    FROM    OKOANIC    MIXTURES.  235 

tion  may  now  be  treutcd  with  a  lew  (lro|)s  of  liydrocliloric  acid 
and  exposed  to  a  current  of  sulphuretted  hydrogen  gas,  when  any 
sulphide  of  antimony  thrown  down  will  exhibit  its  characteristic 
color. 

By  this  method  the  sulphide  of  antimony  produced  from  the 
1-1 00th  of  a  grain  of  the  sesquioxide  of  the  metal  may  be  recovered 
from  a  very  complex  organic  mixture  without  any  apparent  loss. 
Should  the  final  solution  obtained  by  the  above  method  be  highly 
colored,  then,  instead  of  treating  it  with  sulphuretted  hydrogen,  it 
may  be  mixed  with  zinc  and  diluted  sulphuric  acid  in  the  aj)i)aratus 
of  Marsh,  and  the  evolved  gas  conducted  into  a  solution  of  silver 
nitrate,  as  long  as  a  black  precipitate  is  produced.  Any  antimonide 
of  silver  thus  obtained  is  collected  on  a  small  filter  and  well  washed  ; 
the  point  of  the  filter  is  then  pierced,  and  the  precipitate  washed,  by 
means  of  a  jet  of  water  from  a  wash-bottle,  into  a  small  dish,  then 
boiled  with  a  little  tartaric  acid,  the  solution  filtered,  and,  after  con- 
centration if  necessary,  examined  in  the  usual  manner.  The  sulphide 
representing  the  1-lOOth  of  a  grain  of  sesquioxide  of  antimony  may 
be  carried  through  both  these  processes  and  still  yield  perfectly  satis- 
factory results. 

If  it  be  desired,  in  case  the  investigation  for  antimony  should 
fail,  to  provide  for  the  detection  of  other  poisonous  metals  whose 
sulphides  are  also  precipitated  from  acidified  solutions  by  sulphuretted 
hydrogen,  such  as  arsenic,  mercury,  lead,  and  copper,  the  following 
method  may  be  pursued.  The  filter  containing  the  washed  and  still 
moist  precipitate  is  spread  out  in  a  dish,  the  deposit  well  stirred  with 
a  solution  of  yellow  sulphide  of  ammonium,  and  the  solution  filtered. 
As  the  sulphides  of  antimony  and  arsenic  are  readily  soluble  in  sul- 
phide of  ammonium,  these  metals  if  present  would  be  in  the  filtrate, 
while  the  sulpirides  of  mercury,  lead,  and  copper,  being  insoluble  in 
this  menstruum,  would  remain  on  the  filter,  which  should  therefore 
be  reserved  for  future  examination  if  necessary.  The  ammoniacal 
filtrate  is  now  evaporated  to  dryness,  and  the  residue  treated  with 
nitric  acid  anc\  potassium  hydrate  in  the  manner  already  described. 
Any  arsenic  present  would  now  exist  as  arsenate  of  potassium,  and 
the  solution  when  treated  with  sulphuretted  hydrogen  would  yield  a 
yellow  precipitate  of  pentasulphide  of  arsenic.  If  this  metal  was  not 
present,  and  the  mixture  contained  antimony,  the  results  already 
described  would  of  course  be  obtained.     Should  these  two  metals 


236  ANTIMONY. 

occur  in  the  same  solution,  they  may  be  separated  by  treating  the 
mixture  with  zinc  and  sulphuric  acid  and  receiving  the  evolved  gas 
in  a  solution  of  silver  nitrate,  in  the  manner  heretofore  pointed  out. 

From  the  Tissues. — The  investigations  of  Orfila  and  others  have 
shown  that  antimony,  when  taken  into  the  stomach,  is  rapidly 
absorbed  by  the  blood  and  deposited  in  the  tissues,  and  that  the 
absorbed  poison  may  be  entirely  eliminated  from  the  living  body 
within  a  very  few  days,  the  elimination  taking  place  chiefly  through 
the  urine.  Of  the  different  tissues  of  the  body,  the  liver  and  kidneys 
usually  contain  the  largest  proportion  of  the  absorbed  poison. 

About  one-third  of  the  liver,  cut  into  very  small  pieces  and 
placed  in  a  porcelain  dish,  may  be  made  into  a  thin  paste  with  water 
containing  about  one-fifth  of  its  volume  of  pure  hydrochloric  acid. 
The  mixture  is  then  exposed  to  a  moderate  heat,  with  frequent  stir- 
ring and  the  occasional  addition  of  small  quantities  of  powdered 
potassium  chlorate,  until  the  organic  solids  have  become  entirely 
disintegrated.  The  cooled  mixture  is  transferred  to  a  muslin 
strainer,  and  the  organic  matter  left  upon  the  cloth  well  washed 
with  water,  the  washings  being  collected  with  the  first-strained 
liquid ;  the  solution  is  then  filtered,  the  filtrate  concentrated,  allowed 
to  cool,  and  if  necessary  again  filtered.  The  solution  is  now  ex- 
posed for  several  hours  to  a  slow  stream  of  sulphuretted  hydrogen 
gas,  after  which  it  is  allowed  to  repose  for  about  twenty-four  hours, 
in  order  that  the  precipitate  may  fully  subside.  Any  precipitate 
thus  obtained  is  collected,  heated  with  nitric  acid,  then  fused  with 
potassium  hydrate,  and  the  residue  examined  in  the  manner  described 
above. 

For  the  recovery  of  absorbed  antimony,  Orfila  recommended  to 
decompose  the  organic  matter  by  nitric  and  sulphuric  acids.  The 
tissue,  cut  into  small  pieces,  is  boiled  with  nitric  acid,  the  homoge- 
neous mixture  evaporated  to  dryness,  and  the  residue  well  charred 
with  concentrated  sulphuric  acid.  The  dry  carbonaceous  mass  is 
then  boiled  with  hydrochloric  acid  containing  a  few  drops  of  nitric 
acid,  when  any  antimony  present  will  be  dissolved  as  chloride.  The 
solution  thus  obtained  is  introduced  into  the  apparatus  of  Marsh, 
and  the  evolved  gas  examined  in  the  usual  manner. 

Absorbed  antimony  may  also  be  recovered  by  boiling  the  finely 
divided  tissue  with  pure  hydrochloric  acid  diluted  with  about  six 
volumes  of  water,  and  introducing  into  the  boiling  mixture  separate 


SEPAKATION    FROM    ORGANIC    MIXTURES.  237 

slips  of"  briglit  copper-foil  as  long  as  they  continue  to  receive  a 
metallic  coating.  Only  a  small  slip  of  the  copper  should  at  first  be 
employed.  Should  this  after  several  minutes  fail  to  receive  a  de- 
posit, it  is  removed  from  the  mixture,  and  the  boiling  continued 
until  the  organic  tissue  is  entirely  disintegrated.  The  cooled  mix- 
ture is  then  strained,  and  the  strained  liquid  again  boiled  with  a 
fresh  slip  of  copper,  the  heat  being  continued  if  necessary  until  the 
liquid  is  evaporated  to  near  dryness.  It  may  be  remarked  that  this 
method  would  not  apply  to  organic  mixtures  which  had  been  pre- 
pared by  means  of  potassium  chlorate,  since  the  products  of  this 
salt  would  prevent  the  deposition  of  the  antimony. 

Froni  the  Uinne. — Evaporate  one  thousand  grains  of  the  urine  to 
a  thick  syrup;  treat  the  residue  on  a  water-bath  with  fuming  nitric 
acid,  portions  at  a  time,  until  the  urea  is  entirely  destroyed,  then 
evaporate  to  dryness.  Moisten  the  residue  with  concentrated  sul- 
phuric acid,  and  heat  on  a  sand-bath  until  the  mass  is  dry  and 
fumes  of  the  acid  no  longer  escape.  Heat  the  powdered  residue 
with  about  one  hundred  and  twenty-five  grains  of  water  containing 
a  few  drops  of  hydrochloric  acid  until  the  soluble  matter  is  ex- 
hausted ;  filter,  and  concentrate  tlie  filtrate  to  about  eighty  grain- 
measures.  Treat  the  liquid  with  sulphuretted  hydrogen,  and  gently 
warm  the  mixture:  if  the  urine  contained  l-250th  grain  or  more 
of  antimony,  the  precipitate  produced  will  have  a  strongly  marked 
red  color. 

Collect  the  precipitate  on  a  small  filter,  and  wash  it  with  water, 
small  portions  at  a  time,  until  any  calcium  sulphate  and  other  salts 
that  may  have  separated  are  dissolved.  Separate  the  portion  of  the 
filter  containing  the  deposit  from  any  unstained  portion,  and  spread 
it  in  a  porcelain  dish;  add  a  few  drops  of  hydrochloric  acid,  and 
heat  until  the  deposit  has  dissolved,  then  add  a  little  water,  squeeze 
and  wash  the  paper.  Filter,  and  treat  the  filtrate  with  sulphuretted 
hydrogen,  when  any  antimony  present,  even  if  only  in  very  minute 
quantity,  will  be  precipitated  as  sulphide  of  its  characteristic  color. 

By  this  method  we  have  recovered  the  1-lOOOth  of  a  grain  of 
antimony  from  one  thousand  grains  of  urine  (1  :  1,000,000)  without 
any  very  marked  loss. 

In  a  series  of  experiments  on  the  elimination  of  this  metal  by 
means  of  the  urine,  conducted  in  the  University  laboratory  by  Dr. 
Wm.  R.  Hock  ( Thesis),  single  doses  of  ten  milligrammes  (about  one- 


238  ANTIMONY. 

sixth  grain)  each  of  antimony  in  solution  were  taken  or  adminis- 
tered. In  one  instance  the  urine  voided  within  jive  minutes  after 
the  dose  had  been  taken  furnished  satisfactory  evidence  of  the  pres- 
ence of  the  metal ;  and  in  several  instances  it  was  detected  in  from 
ten  to  fifteen  minutes  after  being  taken.  The  greatest  elimination 
seemed  to  take  place  within  from  one  to  two  hours,  after  which  it 
gradually  diminished,  but  traces  were  still  found  as  late  as  ninety- 
six  hours  after  the  dose  had  been  taken. 

Quantitative  Analysis. — The  pure  solution,  acidulated  with 
hydrochloric  acid,  is  treated  with  sulphuretted  hydrogen  gas  as  long 
as  a  precipitate  is  produced,  and  the  mixture  gently  warmed  until 
the  supernatant  liquid  has  become  perfectly  clear.  The  precipitate 
is  then  collected  on  a  filter  of  known  weight,  washed,  thoroughly 
dried  on  a  water-bath,  and  weighed.  Every  one  hundred  parts  by 
weight  of  sesquisulphide  of  antimony  thus  obtained  correspond  to 
85.88  of  the  sesquioxide,  or  196.47  parts  of  pure  crystallized  tartar 
emetic. 


Al^SKMC.  2.'i9 


CHAPTER  Y. 

ARSENIC. 
I.  Metallic  Arsenic. 

History  and  Chemical  Nature. — By  the  term  arsenic  the  chemist 
understands  a  certain  simple  or  elementary  form  of  matter,  having 
metallic  properties;  this  term,  however,  is  popularly  applied  to  an 
oxide  of  tiie  metal, — nrsenious  oxide.  The  symbol  for  arsenic  is 
As;  and  its  atomic  weight  75.  Arsenic  is  found  in  nature  in  certain 
localities  in  its  free  state;  in  combination  it  is  widely  distributed, 
being  found  in  certain  minerals  and  ores,  and  in  minute  traces  in 
many  mineral  waters  and  their  ferruginous  deposits.  The  state- 
ment formerly  made  by  Orfila,  that  arsenic  occurred  as  a  normal 
constituent  in  the  bones  and  muscles  of  animals,  was  afterward 
retracted  as  incorrect. 

In  its  pure  state  arsenic  has  a  steel-gray  color,  a  bright  metallic 
lustre,  and  a  density  of  about  5.8  ;  it  has  a  crystalline  structure,  and 
is  readily  reduced  to  powder,  being  veVy  brittle.  It  remains  un- 
changed in  dry  air;  but  in  the  presence  of  moisture  it  slowly  absorbs 
oxygen  and  assumes  a  dull  dark-gray  appearance.  When  heated,  it 
volatilizes,  without  fusing,  into  a  colorless  vapor,  which  on  coming 
in  contact  with  the  air  emits  a  garlic-like  odor;  if  strongly  heated 
in  the  open  air,  it  takes  fire  and  burns  with  a  bluish  flame  and  the 
evolution  of  dense  white  fumes  of  arsenious  oxide.  It  is  generally 
stated  that  arsenic  volatilizes  at  a  temperature  of  about  182°  C. 
(360°  F.),  but,  according  to  Dr.  Guy,  when  in  small  quantity,  it 
sublimes  at  110°  C.  (230°  F.).  Hot  sulphuric  and  nitric  acids  oxi- 
dize and  dissolve  the  metal,  the  former  as  arsenious  and  the  latter  as 
arsenic  acid.  Hydrochloric  acid  has  no  action  upon  it;  but  free 
chlorine  converts  it  into  chloride  of  arsenic. 


240  AESENIC. 

Physiological  Effects. — Metallic  arsenic,  when  taken  into  the  sys- 
tem, is  capable  of  acting  as  a  powerful  poison ;  but  perhaps  only  in 
so  far  as  the  metal  becomes  oxidized  and  converted  into  arsenious 
acid.  From  the  experiments  of  Bayen  and  Deyeux,  and  others,  it 
would  appear  that  the  metal  in  its  uncombined  state  is  inert.  The 
substance  sold  in  the  shops  under  the  name  of  fly-powder  consists 
essentially  of  a  mixture  of  metallic  arsenic  and  arsenious  oxide,  the 
latter  usually  being  present,  it  is  said,  in  the  proportion  of  about  five 
per  cent.  Numerous  instances  of  poisoning  by  this  substance  have 
occurred,  chiefly,  however,  as  the  result  of  accident.  In  a  case  of 
criminal  poisoning  by  fly-powder,  in  which  we  were  consulted, 
death  took  place  in  thirty-six  hours ;  and  although  there  had  been 
almost  incessant  vomiting  for  over  thirty  hours,  a  quantity  of  ar- 
senic equivalent  to  forty-two  grains  of  arsenious  oxide  remained 
in  the  stomach  at  the  time  of  death.  The  symptoms  and  morbid 
changes  produced  by  this  substance  are  much  the  same  as  those 
occasioned  by  arsenious  oxide. 

Special  Chemical  Properties. — There  is  little  difficulty  in  recog- 
nizing metallic  arsenic.  When  volatilized  in  a  narrow  reduction- 
tube  it  condenses  in  the  cooler  portion  of  the  tube,  forming  a  very 
characteristic  sublimate.  This  sublimate  usually  consists  of  two 
well-defined  but  conjoined  parts,  the  lower  of  which  has  a  steel-like 

appearance,  and  when  viewed  on  the  in- 
FiG.  4.  side  presents  a  crystalline  structure,  re- 

A  sembling    somewhat    that   of    fractured 

iron;  the  upper  part  of  the  deposit, 
when  viewed  exteriorly,  is  destitute  of 
lustre,  and  of  a  dark  color,  which  grad- 
ually fades  into  a  light-gray  margin,  in 
Tubes  for  sublimation  of  arsenic.        which    crystals    of  arscnious    oxidc   are 

sometimes  found.  When  the  sublimate 
is  quite  thin  it  presents  a  brown  appearance.  On  the  application  of 
heat,  the  sublimate  is  readily  chased  up  and  down  the  tube,  and 
sooner  or  later  becomes  converted  into  white,  octahedral  crystals  of 
arsenious  oxide  ;  this  conversion  is  much  hastened  if  the  closed  end 
of  the  tube  has  been  separated.  These  reactions  are  peculiar  to 
arsenic. 

If  metallic  arsenic  be  dissolved,  by  the  aid  of  heat,  in  strong 
nitric  acid,  and  the  solution  evaporated  to  dryness,  it  leaves  a  white 


ARSENIOUS   OXIDE. — ARSENIOUS    ACID.  241 

residue  of  arsenic  oxide,  whicli,  when  moistened  witli  a  strong  solu- 
tion of"  silver  nitrate,  assumes  a  brick-red  color.  A  portion  of"  the 
arsenic  oxide  obtained  by  this  method  may  be  dissolved  in  water  and 
submitted  to  the  liquid' tests  for  this  acid,  mentioned  hereafter;  or, 
the  solution  may  be  saturated  with  sulphurous  oxide  gas  (SOg),  the 
excess  of  the  gas  expelled  by  heat,  and  the  solution  then  examined 
for  arsenious  acid. 

Compounds  of  Ai'senic. — Arsenic  forms  with  oxygen  two  well- 
defined  oxides, — namely,  arsenious  oxide,  AsgOj,  and  arsenic  oxide, 
AsoO..  The  hydrates  of  these  oxides  are  known  respectively  as 
(irscnious  acid  and  arsenic  acid.  A  lower,  or  suboxide,  has  been 
described,  but  its  existence  is  doubtful.  Arsenic  unites  with  sulphur 
in  several  proportions;  the  most  important  of  these  compounds  are 
disulphide  of  arsenic,  or  Bealgar,  As^^i  which  has  a  ruby-red  color; 
sesquisulphide  of  arsenic,  or  Orpiment,  AS2S3,  having  a  bright  yel- 
low color;  and  pentasulphide  of  arsenic,  AsgSg,  the  color  of  which 
closely  resembles  that  of  orpiment.  With  hydrogen  the  metal  forms 
arsenuretted  hydrogen,  or  hydrogen  arsenide,  AsHg,  which  is  a 
colorless,  highly  poisonous,  gaseous  compound.  With  chlorine  it 
forms  trichloride  of  arsenic,  AsClg.  Arsenic  also  enters  into  various 
other  combinations. 

All  the  soluble  compounds  of  this  metal,  and  such  insoluble 
combinations  as  undergo  decomposition  when  taken  into  the  system, 
are  poisonous.  As  a  general  rule,  their  activity  in  this  respect  is  in 
proportion  to  their  solubility.  Some  of  the  insoluble  compounds  as 
usually  met  with  not  unfrequently  contain  arsenious  oxide.  This  is 
the  only  compound  of  the  metal  that  will  be  considered  in  detail;  in 
its  consideration,  however,  the  chemical  properties  of  several  of  the 
other  compounds  will  be  very  fully  described. 

II.  Arsenious  Oxide. — Arsenious  Acid. 

Arsenious  oxide,  commonly  called  white  arsenic,  and  also  known 
as  ratsbane,  is  a  compound  of  two  atoms  of  arsenic  with  three  of 
oxygen,  AsgOg ;  its  molecular  weight  is  99.  It  is  readily  obtained  by 
volatilizing  metallic  arsenic  in  a  free  supply  of  air.  For  commer- 
cial purposes,  it  is  usually  prepared  by  roasting  some  one  of  the  ores 
of  the  metal  in  a  reverberatory  furnace  communicating  with  large 
chambers,  in  which  the  oxide  condenses. 

Arsenious  oxide  is  found  in  the  shops  under  two  different  forms, 

16 


242  AESENIC. 

— either  as  a  white  or  dull  white,  opaque  powder,  or  in  the  form  of 
large,  hard  masses.  If  recently  prepared,  these  masses  are  colorless 
and  transparent ;  but  on  exposure  to  the  air  they  become  opaque 
and  of  a  white  or  yellowish-white  color.  This  change  from  the 
transparent  to  the  opaque  state  has  been  ascribed  to  the  absorption 
of  moisture. 

The  powder,  as  found  in  the  shops,  when  examined  under  the 
microscope,  is  sometimes  wholly  amorphous,  consisting  of  very  fine 
dust  and  small  fragments,  it  being  prepared  simply  by  pulverizing 
the  large  masses.  At  other  times  it  consists  in  part  or  wholly  of 
miimte  octahedral  crystals,  these  ranging  in  size  from  about  l-250th 
to  l-5000th  of  an  inch  in  diameter.  Hence  the  microscopic  char- 
acter of  the  powder — as  to  whether  crystalline  or  not,  the  relative 
proportion  of  crystals  to  amorphous  matter,  and  the  prevailing  size 
of  the  crystals  or  lumps — may  in  some  instances  enable  us  to  de- 
termine with  great  certainty  that  a  given  sample  was  not  derived 
from  a  certain  source  or  supply.  It  has  been  found  by  several 
observers  that  great  uniformity  generally  exists  among  samples  of 
the  powder  taken  from  the  same  source,  as  from  different  and  distant 
parts  of  the  same  keg.  For  examinations  of  this  kind,  it  is  best  to 
mount  a  small  portion  of  the  powder  in  Canada  balsam.* 

Arsenious  oxide,  whether  in  the  solid  state  or  in  solution,  seems 
to  be  nearly  or  entirely  destitute  of  taste.  At  least,  it  has  frequently 
been  swallowed  in  large  quantity  without  any  marked  taste  being 
perceived ;  in  other  instances,  however,  its  taste  has  been  variously 
described  as  sweetish,  rough,  hot,  acrid,  or  metallic. 

Symptoms. — These  are  subject  to  great  variation.  Sooner  or  later 
after  a  large  dose  of  the  poison  has  been  swallowed  there  is  usually 
a  sense  of  heat  and  constriction  in  the  throat,  with  thirst,  nausea, 
and  burning  pain  in  the  stomach.  The  pain  becomes  excruciating, 
and  is  attended  with  violent  vomiting  and  retching ;  the  matters 
vomited  present  various  appearances,  being  sometimes  streaked  with 
blood,  and  at  other  times  of  a  bilious  character;  the  pain  in  the 
stomach  is  increased  by  pressure.  As  the  case  progresses,  the  pain 
extends   throughout   the   abdomen,  and   there   is  generally  severe 


*For  a  very  full  consideration  of  -the  microscopic  differences  observed  in 
samples  of  commercial  arsenic,  we  would  refer  the  reader  to  a  valuable  paper  by 
Prof.  E.  S.  Dana,  of  New  Haven.     {Pamphlet,  1880.) 


PHYSIOLOGICAL   EFFECTS.  243 

pur^'ingaiul  tenesmus;  tlic  matters  j)assed  from  the  bowels  not  unfre- 
qiiently  contain  blood.  Tlic  thirst  usually  becomes  very  intense;  in 
some  instances  there  is  i»;reat  (iilliciilty  of  swallowing.  Tije  features 
are  collapsed  and  expressive  of  great  anxiety ;  the  pulse  is  quick, 
small,  and  irregular;  the  eyes  red ;  the  tongue  dry  and  furred;  the 
skin  cold  and  clammy,  but  sometimes  hot;  the  respiration  difficult; 
and  sometimes  there  arc  violent  cramps  of  the  legs  and  arms.  The 
urine  is  frequently  diminished  in  quantity,  and  its  passage  attended 
with  great  pain.  Stupor,  delirium,  paralysis,  and  convulsions  have 
also  been  observed.  In  many  instances  death  takes  place  calmly, 
and  the  intellectual  faculties  remain  clear  to  the  last. 

Such  are  the  symptoms  usually  observed  in  poisoning  by  arsenic; 
but  cases  are  reported  in  which  the  abdominal  pain,  thirst,  vomiting, 
and  purging  were  either  very  slight  or  entirely  absent.  In  these 
instances  the  symptoms  are  usually  not  very  unlike  those  commonly 
observed  in  poisoning  by  a  narcotic.  There  is  generally  great  pros- 
tration of  strength,  and  faintness,  or  even  actual  syncope;  often 
convulsions,  and  sometimes  delirium  or  insensibility.  It  was  for- 
merly believed  that  well-marked  gastric  symptoms  were  absent  only 
when  a  very  large  dose  of  the  poison  had  been  taken ;  but  this  is 
by  no  means  always  the  case. 

In  a  case  of  arsenical  poisoning  mentioned  by  Dr.  Christison, 
an  individual  expired  in  five  hours  without  at  any  time  having 
vomited,  although  emetics  were  administered.  The  following  case 
of  this  kind  is  reported  by  Mr.  Fox.  [Lancet,  London,  Nov.  4, 
1848.)  A  stout,  healthy  young  man  took  a  teaspoonful  of  arsenious 
oxide,  mistaking  it  for  flour.  No  marked  symptom  of  the  action 
of  the  poison  appeared  for  nearly  six  hours  afterward,  when  purging 
suddenly  supervened,  and  he  vomited  two  or  three  times.  He  then 
became  drowsy;  countenance  sunken  and  livid;  pulse  rapid  and 
extremely  feeble ;  surface  of  the  body  cold,  and  watery  stools  of  a 
greenish  hue  passed  involuntarily.  He  answ^ered  questions  ration- 
ally, and  did  not  complain  either  of  pain,  tenderness  of  the  abdomen, 
tenesmus,  or  any  of  the  usual  irritative  symptoms  of  arsenical  poison- 
ing. Soon  afterward  he  complained  of  dimness  of  sight,  lay  down 
on  the  bed,  and  in  a  few  minutes  expired. 

In  most  cases  of  acute  poisoning  by  this  substance  the  symp- 
toms steadily  run  their  course ;  yet  sometimes  there  is  a  remission  or 
even  an  entire  intermission  of  the  more  prominent  symptoms.     This 


244  AESENIC. 

remission  may  extend  through  a  period  of  several  hours,  and  the 
symptoms  then  return  with  increased  violence.  The  remission  has 
even  been  repeated  several  times  in  the  same  case. 

The  following  singular  case  is  related  by  Dr.  C.  U.  Shepard,  of 
South  Carolina.  {Pamphlet,  1878.)  An  intemperate  man  purposely 
swallowed,  towards  evening,  about  an  ounce  of  arsenic.  Imme- 
diately after  taking  the  draught  he  vomited  considerably,  and  during 
the  night  at  intervals.  The  next  morning  he  went  into  the  street, 
having  up  to  that  time  experienced  little  or  no  pain.  About  an  hour 
later,  however,  he  was  seized  with  severe  pains  in  the  epigastrium, 
and  fell  on  the  pavement  in  great  agony.  After  a  few  hours  the 
pain  subsided,  and  he  was  comparatively  well.  But  several  hours 
later  he  was  again  seized  with  violent  pain  in  the  stomach,  and  with 
excessive  vomiting  and  purging.  Wild  delirium  and  general  con- 
vulsions then  supervened,  and  terminated  fatally  about  twenty-four 
hours  after  the  poison  had  been  taken. 

Considerable  variety  has  also  been  observed  in  regard  to  the  time 
within  which  the  symptoms  first  manifest  themselves.  In  most 
instances,  however,  they  appear  in  from  half  an  hour  to  an  hour 
after  the  poison  has  been  taken.  In  the  case  just  related,  there  was, 
according  to  the  statement  of  the  patient,  immediate  vomiting.  And 
in  a  case  cited  by  Dr.  Beck,  a  woman,  who  had  swallowed  a  quantity 
of  the  poison  mixed  with  wine  and  an  egg,  experienced  extreme  dis- 
tress immediately  after  taking  the  mixture.  [Med.  Jur.,  ii.  595.)  In 
another  instance,  quoted  by  the  same  writer,  twelve  persons  in  one 
family  were  seized  with  symptoms  immediately  after  eating  some 
soup  containing  the  poison.  Dr.  Christison  quotes  a  case  in  which 
the  symptoms  appeared  in  eight  minutes;  and  two  others  in  which 
violent  symptoms  were  present  in  ten  minutes  after  the  poison  had 
been  taken. 

On  the  other  hand,  instances  are  related  in  which  the  symptoms 
were  delayed  much  beyond  the  usual  period.  A  case  of  this  kind, 
in  w^hich  they  did  not  appear  for  nearly  six  hours,  has  already  been 
cited.  In  a  case  related  by  Dr.  Ryan,  where  half  an  ounce  of  arsenic 
was  taken  in  porter,  the  first  symptom,  which  was  vomiting,  did  not 
occur  until  nine  hours  afterward.  (Wharton  and  Still6,  31ed.  Jur., 
513.)  A  case  is  also  quoted  by  Dr.  Taylor,  from  Belloc,  in  which 
ten  hours  elapsed  before  any  symptoms  appeared.  {On  Poisons,  359.) 
And  Dr.  Wood  mentions  an  instance  {U.  S.  Dispensatory,  1865,  26), 


EFFECTS   OF    EXTERNAL    APPLrCATIDN.  245 

related  l>v  Dr.  K.  Hartsliornc,  in  wliidi  at  least  a  drachm  of  arseni- 
ous  oxide  had  been  swallowetl,  and  where  the  syniptoius  of  poisoning 
wore  delayed  for  sixteen  hours.  This  seeras  to  be  the  most  protracted 
case,  in  this  respect,  yet  recorded. 

The  external  application  of  arsenic  to  abraded  surfaces  has  not 
unfrcquently  been  followed  by  fatal  results.  In  a  case  reported  by 
Dr.  McCready,  a  wash  composed  of  a  mixture  of  arsenious  oxide 
and  i;in,  applied  to  the  head  of  a  child  two  years  old,  affected  with 
porrigo  favosa,  caused  death  in  about  thirty-six  hours.  The  most 
prominent  symptoms  were  swelling  of  the  face,  purging  and  tenesmus, 
and  paralysis  of  the  lower  extremities.  No  local  inflammation  was 
produced.  Two  other  children  who  were  similarly  treated  suffered 
with  redness  and  swelling  of  the  face ;  but  they  speedily  recovered. 
[Am.  Jour.  Med.  Sci.,  July,  1851,  259.)  Dr.  Christison  cites  an 
instance  in  which  the  stearine  of  a  candle  containing  arsenic,  applied 
to  a  blistered  surface,  produced  local  pain,  nausea,  pain  in  the  stomach, 
great  thirst,  redness  of  the  tongue,  spasms  of  the  muscles  of  the 
lower  extremities,  and  weakness  and  irregularity  of  the  pulse,  fol- 
lowed by  death  within  twenty-four  hours  after  the  application  had 
been  made. 

In  a  series  of  cases  recently  reported  (1878),  a  mixture  sold  as 
violet  poicder,  containing  nearly  fifty  per  cent,  of  arsenic, — ignorantly 
substituted  for  gypsum,  and  this  used  instead  of  starch, — applied  exter- 
nally to  some  twenty-eight  infants,  caused  death  in  thirteen  instances. 
All  the  children  suffered  more  or  less  from  the  application.  The 
symptoms  were  a  reddened  condition  of  the  skin,  which  soon  became 
blue  or  black,  and  vesicated ;  there  was  great  restlessness,  with  fits 
of  screaming,  followed  by  collapse  and  quiet  death.  The  average 
duration  of  the  fatal  cases  was  from  four  to  five  days. 

Arsenic  has  also  proved  fatal  when  applied  to  the  mucous  mem- 
brane of  the  vagina  and  of  the  rectum,  and  when  inhaled  in  the  form 
of  vapor.  In  a  case  reported  by  Dr.  Mangor,  a  man  poisoned  three 
waves  in  succession  by  introducing  arsenic  into  the  vagina.  In  at 
least  two  of  these  instances  the  poison  produced  its  usual  symptoms 
and  death  in  twenty-four  hours.  Within  late  years  numerous  in- 
stances of  chronic  poisoning  by  this  substance  have  occurred  from 
pereons  occupying  rooms  hung  with  paper  stained  with  Scheele's 
green,  or  arsenite  of  copper.  From  the  examination  of  twenty-one 
cases  of  poisoning  of  this  kind.  Dr.  Kirchgasser,  of  Coblentz,  con- 


246  ARSENIC. 

eludes  that  the  deleterious  eflFects  are  due  to  the  mechanical  suspen- 
sion of  arsenical  dust  in  the  air  of  the  apartment,  rather  than  to  the 
presence  of  a  volatile  arsenical  compound,  as  some  have  supposed. 
{Sydenham  Soc.  Year-Booh,  1869,  446.) 

Period  when  Fatal. — In  fatal  poisoning  by  this  substance,  death 
usually  occurs  in  from  twelve  to  thirty-six  hours  after  the  poison 
has  been  taken.  Numerous  instances,  however,  are  related  in  which 
death  took  place  within  a  very  few  hours ;  while,  on  the  other  hand, 
life  has  not  unfrequently  been  prolonged  for  several  days.  The  most 
rapidly  fatal  case  yet  recorded  is  that  communicated  to  Dr.  Taylor, 
in  which  a  youth,  aged  seventeen,  died  from  the  eflFects  of  a  large 
dose  of  the  poison  within  twenty  minutes  after  it  had  been  taken. 
{Med.  Jur.,  i.  256.)  Dr.  D.  W.  Finlay  has  recently  reported  a  case 
fatal  in  one  hour  from  the  eflPects  of  a  solution  containing  upwards 
of  twenty-six  grains  of  arsenious  oxide.  In  this  case  there  was 
profound  collapse,  with  only  slight  symptoms  of  irritation.  {Lancet, 
Dec.  1883,  943.)  Not  less  than  three  instances  fatal  in  two  hours  are 
reported.  In  a  case  related  by  Dr.  Dymock,  death  occurred  in  two 
hours  and  a  half;  and  Pyl  relates  another,  which  proved  fatal  in 
three  hours.  {Christison  on  Poisons,  240.)  Ninety  grains  of  the 
poison  caused  the  death  of  a  girl,  aged  fourteen  years,  in  five  hours. 
Several  instances  are  reported  in  which  the  patients  recovered  from 
the  primary  action  of  the  poison  and  died  from  its  secondary  effects 
very  long  periods  afterward,  even  in  one  instance,  related  by  Wepfer, 
after  the  lapse  of  three  years. 

Fatal  Quantity. — According  to  the  observations  of  Prof.  Lach&se, 
of  Angers,  a  dose  of  from  one  to  two  grains  of  arsenious  oxide  may 
prove  fatal  to  a  healthy  adult;  a  dose  of  from  a  quarter  to  half  a 
grain  may  induce  symptoms  of  poisoning ;  and  one-eighth  of  a  grain 
may  prove  injurious.  In  a  case  quoted  by  Dr.  Taylor,  two  grains  of 
the  poison,  in  the  form  of  Fowler's  solution,  taken  in  divided  doses 
during  a  period  of  five  days,  destroyed  the  life  of  a  woman.  The 
same  writer  cites  another  instance,  reported  by  Dr.  Letheby,  in  which 
two  grains  and  a  half  killed  a  robust,  healthy  girl,  aged  nineteen,  in 
thirty-six  hours.  {On  Poisons,  377.)  In  a  case  mentioned  by  Dr. 
Christison,  four  grains  and  a  half  caused  the  death  of  a  child,  four 
years  old,  in  six  hours. 

On  the  other  hand,  recovery  has  not  unfrequently  taken  place 
after  very  large  quantities  of  the  poison  had  been  swallowed.     In  a 


ANTIDOTES.  247 

case  recorded  by  Dr.  Pereira,  a  man  swallowed  half  an  ounce  of 
powdered  arsenics  iinmediately  after  takin<^  his  dinner,  and  the  only 
effect  produced  was  violent  vomiting.  {Mat.  3fed.,  i.  032.)  So,  also, 
Dr.  A.  Stillo  {3fat.  Med.,  ii.  707)  quotes  the  case  of  a  woman  who 
.swallowed  about  a  dessertspoonful  of  the  poison  immediately  after  a 
hearty  meal,  and  although  vomiting  did  not  occur,  nor  were  any 
remedies  administered  for  an  hour  and  a  half,  yet  within  five  days 
complete  recovery  had  taken  place. 

The  following  remarkable  case  is  reported  by  Dr.  AV.  C.  Jackson. 
{Am.  Jour.  Med.  Sci.,  July,  1858,  77.)  A  young  man,  aged  twenty- 
eight  vears,  took  on  an  empty  stomach  not  less  than  ttvo  ounces  of 
the  poison.  Nearly  two  hours  afterward  there  was  slight  vomiting, 
with  some  traces  of  the  arsenic;  but  the  greater  part  of  the  poison 
was  retained  in  the  body  for  six  hours.  Great  irritability  of  the 
stomach  then  ensued,  with  a  burning  sensation  in  this  organ  and  in 
the  throat.  This  condition  continued  for  about  six  hours,  after  which 
the  patient  rapidly  recovered. 

In  a  case  quoted  by  Prof.  H.  C.  Wood  {3fat.  Med.  and  Toxicol., 
1874,  320),  a  man  swallowed  an  unknown  quantity  of  arsenic  in 
lumps,  and  received  no  treatment  for  sixteen  hours,  yet  recovered 
after  passing  per  anum  one  hundred  and  five  grains  of  arsenic  in 
two  masses. 

Treatment. — This  consists,  in  the  first  place,  if  there  is  not 
already  free  vomiting,  in  the  speedy  administration  of  an  emetic,  or 
the  stomach  may  be  emptied  by  means  of  the  stomach-pump.  As  an 
emetic,  sulphate  of  zinc  or  of  copper  may  be  employed ;  if  neither 
of  these  is  at  hand,  powdered  mustard  or  a  mixture  of  salt  and  water 
should  be  administered,  or  vomiting  may  be  induced  by  tickling  the 
throat  with  a  feather.  The  vomiting  should  be  assisted  by  the  free 
exhibition  of  demulcent  drinks.  For  this  purpose  a  mixture  of  milk 
and  white  of  egg  has  been  found  very  beneficial.  If  the  poison  has 
passed  into  the  bowels,  a  dose  of  castor  oil  may  be  highly  useful. 

Of  the  various  chemical  antidotes  that  have  been  proposed  for 
arsenious  acid,  hydrated  ferric  oxide,  known  also  as  hydrated  sesqui- 
oxide  of  iron,  FcoOgjoHoO,  is  much  the  most  important.  Drs.  Bun- 
sen  and  Berthold,  in  1834,  were  the  fii-st  to  assert  the  antidotal 
properties  of  this  substance.  When  it  is  added  to  a  solution  of 
arsenious  acid,  the  latter  is  rendered  wholly,  or  very  nearly,  in- 
soluble in  water.     In  support  of  this  statement  we  may  adduce  the 


248  AESEN-IC. 

following  experiments:  1.  One  grain  of  arsenious  oxide,  in  solu- 
tion, was  agitated  for  a  very  little  time  with  five  grains  of  the  iron 
preparation  suspended  in  half  an  ounce  of  water,  and  the  mix- 
ture quickly  filtered.  The  filtrate  was  then  examined  and  found  to 
contain  less  than  the  1-lOOth  of  a  grain  of  the  poison.  2.  When 
ten  parts  of  the  iron  preparation  were  employed,  and  the  filtrate 
concentrated  to  one  hundred  fluid-grains,  then  acidulated  with  hy- 
drochloric acid,  and  saturated  with  sulphuretted  hydrogen  gas,  it 
failed  to  yield  any  distinct  evidence  of  the  presence  of  the  poison, 
even  after  standing  at  a  moderate  temperature  for  several  hours. 
These  experiments  do  not,  of  course,  prove  that  the  compound  thus 
produced  is  insoluble  in  the  acid  secretions  of  the  stomach ;  yet  the 
excess  of  the  iron  preparation  administered  might  neutralize  any 
free  acid  present. 

The  antidotal  action  of  this  substance  is  due  to  the  hydrated  ferric 
oxide  yielding  a  portion  of  its  oxygen  to  the  arsenious  acid,  whereby 
the  latter  is  converted  into  arsenic  acid,  which  in  turn  unites  with  a 
portion  of  the  iron,  forming  arsenate  of  iron  (Fe32As04),  which  being 
insoluble  is  inert.  Thus :  2Fe203,3H20  +  2H3ASO3  =  Fe32As04  + 
FeO  +  9TI2O.  Theoretically,  therefore,  one  part  of  arsenious  oxide 
in  solution  as  arsenious  acid  requu'es  2.16  parts  of  pure  hydrated 
ferric  oxide  to  render  it  inert.  The  antidote  should,  however,  be 
given  in  its  moist  state,  and  be  administered  in  large  excess.  It  is 
usually  stated  that  about  twelve  parts  of  the  moist  compound  are 
required  for  one  part  of  arsenious  oxide.  The  antidote  has  no 
action  upon  arsenious  oxide  in  its  solid  state,  but  only  when  in 
solution. 

Hydrated  ferric  oxide  may  readily  be  prepared  by  treating  tinc- 
ture of  ferric  chloride  of  the  shops,  or  a  strong  solution  of  ferric  sul- 
phate, with  slight  excess  of  ammonia,  collecting  the  precipitate  on  a 
muslin  strainer,  and  washing  it  with  water  until  it  no  longer  emits 
the  odor  of  ammonia.  A  tablespoonful  or  more  of  the  moist  magma, 
mixed  with  a  little  water,  may  be  given  at  a  dose.  The  antidote 
should  always  be  freshly  prepared. 

In  this  connection,  we  may  very  briefly  refer  to  some  experi- 
ments, kindly  undertaken  by  Dr.  Wm.  Watt,  with  this  antidote  upon 
poisoned  dogs.  (For  details,  see  Ohio  Med.  and  Surg.  Jour.,  March, 
1861.)  The  action  of  the  poison  alone  was  first  determined  upon 
five  dogs  of  average  size.     To  three  of  these,  six  grains  of  arsenious 


ANTIDOTES.  249 

oxide,  ill  solution,  were  i^iven  to  euoli,  and  proved  futiil  in  one  hour 
and  II  half,  five  hours,  and  six  hours  respectively.  To  the  otiier  two, 
three  grains  each  were  administered,  and  caused  death  in  six  and 
eiglit  hours  respectively.  A  solution  of  the  poison  was  then  adminis- 
tered to  twelve  other  dogs,  and  the  dose  followed — in  some  instances 
immediately,  in  others  in  ten  minutes,  and  in  others  still  not  until 
symptoms  of  poisoning  had  manifested  themselves — by  a  single  dose 
of  about  two  tablespoonfuls  of  the  antidote,  prepared  in  the  manner 
just  described.  After  vomiting,  in  some  instances  only  once,  but  in 
others  several  times,  all  these  animals  recovered,  at  most  within  sev- 
eral hours,  and  without  in  any  instance  suffering  severe  symptoms. 
Two  of  these  dogs  received  three  grains;  two,  four  grains;  one,  five 
grains ;  three,  six  grains ;  two,  seven  grains ;  and  two,  eight  grains 
each  of  the  poison.  In  another  experiment,  six  grains  of  the  poison, 
in  solution,  were  mixed  with  about  fifteen  parts  by  weight  of  the 
antidote,  and  the  mixture,  after  standing  twenty  minutes,  given  to 
a  dog;  no  appreciable  effect  whatever  was  observed,  although  the 
animal  was  closely  watched  for  many  hours.  This  experiment, 
therefore,  indicates  that  the  arsenate  of  iron  is  not  readily  decom- 
posed by  the  juices  of  the  stomach. 

Numerous  instances  are  reported  in  which  there  seems  to  be  no 
doubt  that  this  antidote  was  the  means  of  saving  life  iu  the  human 
subject.  Mr.  Robson  relates  an  instance  of  this  kind,  in  which 
more  than  a  drachm  and  a  half  of  the  poison  had  been  swallowed, 
and  the  antidote  was  not  administered  until  two  hours  after  the 
poison  had  been  taken.  In  this  case,  about  an  hour  after  the  inges- 
tion of  the  poison,  the  stomach-pump  was  used,  but  unsuccessfully, 
on  account  of  the  instrument  becoming  choked  with  the  remains  of 
food.  [U.  S.  Dispensatory,  1865,  29.)  It  need  hardly  be  remarked 
that  the  antidote  can  have  no  effect  upon  any  of  the  poison  that  has 
already  entered  the  circulation. 

Instead  of  the  above  antidote,  R.  V.  Mattison  has  advised  [Am. 
Jour.  Pharm.,  Jan.  1878,  23)  a  solution  of  dialyzed  iron,  followed 
immediately  by  the  administration  of  common  salt.  According  to 
E.  Hirschsohn,  of  Dorpat,  however,  dialyzed  iron  is  much  less  cer- 
tain in  its  action  than  the  antidotum  arsenici,  which  consists  of  a 
mixture  of  hydrated  ferric  oxide,  magnesium  sulphate,  and  magne- 
sium hydrate,  being  prepared  by  treating  a  solution  of  ferric  sulphate 
with  excess  of  magnesia. 


250  ARSENIC. 

In  four  cases  of  arsenical  poisoning  reported  by  Dr.  C.  A.  Leale, 
of  New  York  [Am.  Jour.  Med.  Sci.,  Jan.  1880,  80),  he  employed 
as  an  antidote  the  common  subcarbonate  of  iron  with  good  results, 
although  in  one  instance  fully  one  ounce  of  arsenious  oxide,  and  in 
the  others  one-half  ounce,  one  ounce,  and  two  ounces  respectively  of 
Paris  green  had  been  taken. 

Post-mortem  Appearances. — Great  variety  has  been  observed 
in  the  appearances  after  death  from  arsenic,  even  in  cases  in  which 
the  symptoms  during  life  were  very  similar.  The  lining  membrane 
of  the  throat  and  oesophagus  has  in  some  few  instances  been  found 
highly  inflamed.  The  mucous  membrane  of  the  stomach  is  generally 
more  or  less  reddened  and  inflamed ;  sometimes  it  has  a  deep  crimson 
color,  at  other  times  it  is  of  a  deep  brownish-red,  and  it  has  presented 
a  dark  appearance,  due  to  the  effusion  of  altered  blood.  This  mem- 
brane is  sometimes  much  softened,  and  easily  separated  ;  and  in  some 
instances  patches  of  it  are  entirely  destroyed.  In  other  instances, 
however,  it  is  much  thickened  and  corrugated.  The  inflammation 
rarely  extends  to  the  peritoneal  covering  of  the  stomach.  When  the 
poison  has  been  taken  in  the  solid  state,  small  particles  of  it  are  fre- 
quently found  adhering  to  the  mucous  membrane  and  covered  with 
coagulated  mucus.  Ulceration  of  the  stomach  has  been  of  rare 
occurrence,  except  in  protracted  cases ;  however,  Dr.  Taylor  observed 
it  in  a  case  that  proved  fatal  in  ten  hours. 

In  protracted  cases,  the  intestines,  particularly  the  duodenum  and 
rectum,  not  unfrequently  present  signs  of  inflammatory  action  similar 
to  those  found  in  the  stomach.  The  lungs  are  sometimes  congested 
and  inflamed ;  congestion  of  the  brain  has  also  been  observed.  The 
blood  throughout  the  body  is  usually  liquid,  and  of  a  dark  color. 

Not  a  few  instances  of  poisoning  by  this  substance  are  recorded 
in  which  after  death  no  well-marked  morbid  appearances  were  dis- 
covered in  any  part  of  the  body.  This  result  has  even  been  observed 
in  cases  in  which  there  were  violent  symptoms  and  life  was  prolonged 
for  many  hours. 

In  a  case  reported  by  Dr.  A.  R.  Davidson  {Buffalo  Med.  and 
Surg.  Jour,,  Oct.  1882,  117),  in  which  an  unknown  quantity  of  the 
poison  proved  fatal  in  twelve  hours,  under  the  usual  symptoms,  to  a 
boy  aged  six  years,  the  mucous  membrane  of  the  stomach  was  slightly 
paler  than  normal,  and  wholly  free  from  any  appearance  of  inflam- 
matory action;  nor  was  any  morbid  change  observed  in  any  part  of 


PRI-isERVATIVE   EFFECTS.  251 

the  body.  Something  over  lialf  a  frpain  of  arsenious  oxide  was 
recovered  from  tlie  liver  and  kidneys. 

When  the  inspection  is  made  some  time  after  decomposition  has 
been  established,  the  stomach  and  intestines  may  present  patches  of 
a  more  or  less  brigiit  yellow  color,  due  to  the  conversion  of  the 
arsenic  into  sulphide  by  the  sulphuretted  hydrogen  evolved  in  the 
putrefaction.  This  appearance  may  manifest  itself  within  a  few  days 
after  death,  as  we  have  observed  in  poisoned  animals;  whilst,  on  the 
otiier  hand,  even  when  very  notable  quantities  of  the  poison  are 
present,  it  may  be  absent  after  even  very  long  periods.  Indeed,  it 
has  recently  been  shown  by  J.  Assikovszky  {Jour,  prakt.  Chem., 
1880,  323)  that  during  the  process  of  putrefaction  of  organic  bodies 
pure  arsenious  sulphide  may  be  converted  into  arsenious  and  arsenic 
oxides. 

Antiseptic  Properties  of  Arsenic. — The  preservative  power  of 
arsenic  when  brought  in  direct  contact  with  animal  textures  is  well 
known ;  and  the  poison  seems  to  exert  a  similar  action  when  carried 
by  means  of  the  circulation  to  the  different  tissues  of  the  body.  The 
bodies  therefore  of  those  who  have  died  from  the  effects  of  this 
poison  are  not  unfrequently  found  in  a  good  state  of  preservation, 
even  long  periods  after  death. 

We  have  elsewhere  reported  a  case,  described  by  Dr.  Douglas 
Day,  in  which  this  preservative  action  of  the  poison  was  well  marked 
in  a  body  that  had  been  buried  seventeen  months.  At  this  time  the 
body  was  destitute  of  odor,  and  the  flesh  of  the  extremities  had  given 
place  to  a  dark  unctuous  matter.  The  abdominal  walls  were  in  a 
surprising  state  of  preservation,  and  of  the  color  of  old  parchment; 
the  integuments  upon  incision  were  firm,  and  the  muscles  of  a  pink 
hue,  but  very  attenuated.  The  omentum  was  large  and  in  place,  and 
covered  with  saponaceous  matter.  The  stomach  and  intestines  were 
pale,  comparatively  dry,  and  appeared  as  though  the  convolutions 
had  been  pressed  together;  they  were  firm  and  allowed  free  manipu- 
lation, and  exhaled  a  peculiar  but  not  offensive  odor.  The  liver, 
spleen,  and  pancreas  appeared  remarkably  recent,  and  the  posterior 
walls  of  the  abdomen,  the  mesentery,  and  kidneys  were  well  pre- 
served. The  bladder  also  was  in  a  good  state  of  preservation.  A 
very  notable  quantity  of  arsenic  was  detected  in  each  of  several  of 
the  abdominal  organs :  no  other  parts  were  submitted  to  chemical 
examination.     {Ohio  3Ied.  and  Siwg.  Jour.,  Xov.  1863.) 


252  AESENIC, 

In  another  case  in  which  we  made  the  chemical  examination  in 
1871,  that  of  Peter  Buffenbarger,  of  Ohio,  the  body  when  exhumed, 
at  the  end  of  three  years  and  a  half,  "  was  found  entire  and  in  a 
remarkable  state  of  preservation."  "  The  tissues  were  quite  firm  and 
solid ;  the  liver  entire,  but  easily  broken  up ;  the  stomach  was  fresh 
and  parchment-like;  the  walls  of  the  abdomen  firm."  Very  satis- 
factory evidence  of  the  presence  of  arsenic  in  minute  quantity  was 
obtained  both  from  the  stomach  and  the  liver.  These  were  the  only 
organs  furnished  for  chemical  analysis.  At  a  preliminary  hearing 
of  this  case,  it  was  urged  by  the  defence  that  the  poison  had  been 
injected  into  the  body  after  death.  It  was  clearly  shown,  however, 
that  the  vault  in  which  the  body  was  buried  had  not  been  disturbed 
from  the  time  it  was  first  closed ;  and  there  was  no  evidence  what- 
ever that  the  poison  had  been  injected  before  burial. 

Dr.  Christison  quotes  a  case  in  which  the  body  after  being  interred 
seven  years  was  found  entire.  The  head,  trunk,  and  limbs  retained 
their  situation  ;  but  the  organs  of  the  chest  and  abdomen  were  con- 
verted into  a  brown  soft  mass,  in  which  a  chemical  analysis  revealed 
the  presence  of  a  considerable  quantity  of  arsenic. 

Although  the  bodies  of  those  who  died  from  the  effects  of  this 
poison  have  thus  been  found  in  an  unusual  state  of  preservation,  yet 
this  is  by  no  means  always  the  case,  even  when  the  poison  remains 
in  the  body  at  the  time  of  death.  In  fact,  in  some  cases  of  arsenical 
poisoning  the  process  of  putrefaction  seemed  to  advance  with  in- 
creased activity.  At  the  same  time,  it  must  be  borne  in  mind  that 
the  body  is  sometimes  unusually  preserved  in  cases  in  which  death 
resulted  from  ordinary  disease  or  mechanical  injury. 

Chemical  Properties. 

General  Chemical  Nature. — It  has  already  been  stated  that 
arsenious  oxide,  in  its  amorphous  state,  occurs  under  two  varieties, 
known  as  the  transparent  and  the  opaque.  The  specific  gravity  of 
the  transparent  variety  seems  to  be  some  little  greater  than  that  of  the 
opaque,  the  density  of  the  former,  according  to  most  observers,  being 
about  3.75,  and  that  of  the  latter  about  3.65.  These  varieties  also 
differ  in  regard  to  their  solubility  in  water.  According  to  most  ob- 
servers, arsenious  oxide  volatilizes  at  about  191°  C.  (380°  F.) ;  but, 
according  to  Dr.  Guy,  it  may  be  vaporized,  especially  if  in  minute 
quantity,  at  138°  C.  (280°  F.).    The  vapor  is  colorless  and  odorless, 


SOLUBILITY    IN   WATER.  253 

and  recondenses  nnoIian(;e(l  on  cold  surfaces,  principally  in  the  forn)  of 
regular  octahedral  crystals.  (For  an  excellent  paper  on  the  crystal- 
line ibrms  of  arsenious  oxide,  by  Dr.  Guy,  see  Quart.  Jour.  Micro. 
Science,  July,  1861.) 

Arsenious  oxide  is  soluble  in  water  with  the  formation  of  arsenious 
acid,  each  molecule  of  the  former  assimilating  the  elements  of  three 
molecules  of  water  to  form  two  molecules  of  the  acid;  thus :  AsgOgH- 
3HoO  :=  2H3ASO3.  This  acid,  which  is  tribasic,  has,  however,  not 
yet  been  obtained  in  the  free  state. 

Arsenious  acid  has  only  feebly  acid  properties ;  nevertheless  it 
readily  unites  Avitli  many  of  the  metals,  forming  salts  denominated 
arsenitcs.  These  salts  are  readily  decomjiosed  by  most  other  acids. 
The  arsenites  of  the  alkali  metals  are  freely  soluble  in  water;  but  all 
other  arsenites  are  either  insoluble  or  only  sparingly  soluble  in  this 
menstruum.  The  latter  salts  are  readily  decomposed  and  dissolved 
by  nitric  and  hydrochloric  acids.  Upon  the  application  of  heat, 
most  of  the  arsenites  undergo  decomposition.  In  this  operation  the 
fixed  alkali  arsenites  retain  the  greater  portion  of  the  arsenic,  in  the 
form  of  an  arsenate.  When  ignited  with  a  reducing  agent,  all  ar- 
senites are  decomposed,  with  the  evolution  of  metallic  arsenic  in  the 
form  of  vapor. 

Solubi/ity.  1.  In  Water. — The  degree  of  solubility  of  arsenious 
oxide  in  water  sometimes  becomes  a  matter  of  considerable  importance 
in  medico-legal  investigations.  The  results  of  observers  in  regard 
to  this  point  have  been  extremely  discordant.  The  exact  quantity 
of  the  poison  that  will  be  taken  up  and  retained  in  solution  by 
a  given  quantity  of  water  will  depend  upon  a  variety  of  circum- 
stances, among  the  principal  of  which  are  the  following:  1.  The 
physical  state  of  the  oxide ;  2.  The  relative  proportions  of  the  oxide 
and  water  present ;  3.  The  time  they  have  been  in  contact ;  4.  The 
temperature  of  the  mixture ;  5.  If  the  mixture  has  been  boiled,  the 
length  of  time  the  boiling  was  continued  ;  and,  6.  The  time  that  has 
elapsed  since  the  mixture  was  heated.  Among  numerous  experiments 
that  might  be  cited  showing  the  influence  of  these  various  conditions, 
the  following  may  be  mentioned  : 

a.  One  part  (50  grains)  of  finely  powdered  opaque  arsenious 
oxide  was  boiled  with  ten  parts  (500  grains)  of  distilled  water  for  one 
hour,  the  vaporized  fluid  being  condensed  and  returned  to  the  flask 
as  rapidly  as  formed,  and  thus  the  volume  of  the  fluid   kept  con- 


254  ARSENIC. 

stantly  the  same.  The  solution  was  then  filtered  as  rapidly  as  possible, 
and  a  given  portion  of  the  filtrate  evaporated  to  dryness  on  a  water- 
bath.  The  residue  thus  obtained  indicated  that  one  part  of  the  oxide 
had  dissolved  in  13.10  parts  of  water. 

h.  A  similar  experiment  with  the  transparent  variety  of  the  oxide, 
taken  from  the  same  mass  as  employed  in  experiment  a,  gave  a 
residue  indicating  that  one  part  of  the  oxide  had  dissolved  in  15.66 
parts  of  water.  According  to  Bussy,  the  transparent  variety  is  more 
soluble  than  the  opaque;  Guibourt,  however,  states  that  the  reverse 
is  the  fact. 

c.  A  similar  experiment  with  the  freshly  sublimed  crystallized 
oxide  indicated  that  one  part  of  the  oxide  had  dissolved  in  11.50 
parts  of  water. 

d.  On  repeating  the  last  experiment  and  concentrating  the  filter- 
ing solution  to  about  half  its  volume,  a  white  scum  appeared  upon 
the  surface  of  the  liquid.  The  clear  liquid  was  then  decanted  and 
a  given  portion  evaporated  to  dryness,  when  it  was  found  that  one 
part  of  the  oxide  had  been  held  in  solution  by  6.72  parts  of  water. 

e.  After  boiling  one  part  of  the  crystallized  oxide,  from  the  sam- 
ple used  in  experiment  c,  for  one  hour  with  ten  parts  of  pure  water, 
without  loss  of  liquid  by  evaporation,  the  mixture  was  allowed  to 
stand  twenty-four  hours.  The  solution  then  contained  one  part  of 
the  oxide  in  58.68  parts  of  water. 

/.  One  part  of  the  opaque  oxide,  from  the  sample  used  in  experi- 
ment a,  was  boiled  for  one  hour  with  forty  parts  of  water,  without 
loss  of  liquid  by  evaporation,  and  the  solution  quickly  filtered.  The 
filtrate  contained  one  part  of  the  oxide  in  43.7  parts  of  the  men- 
struum. It  will  be  observed  that  in  this  experiment  the  conditions 
were  the  same  as  in  experiment  a,  except  in  the  relative  proportion 
of  oxide  and  water  present.  Even  when  one  part  of  the  oxide  is 
boiled  for  an  hour  with  one  hundred  parts  of  water,  a  portion  of  the 
poison  will  still  remain  undissolved. 

g.  One  part  of  the  opaque  oxide  was  treated  w^ith  twenty  parts  of 
boiling  water  and  the  mixture  frequently  agitated  for  twenty-four 
hours.  The  solution  then  contained  one  part  of  the  oxide  in  196 
parts  of  water. 

h.  On  treating  the  transparent  variety  of  the  oxide  in  the  same 
manner  as  in  the  last  experiment,  the  solution  contained  one  part  of 
the  poison  in  93  parts  of  the  menstruum.    On  comparing  the  experi- 


SOLUBILITY    IN    WATER.  255 

nients  q  and  /*  with  tliosc  of  a  and  b,  it  will  he  observed  tliat  under 
one  set  of  conditions  the  transparent  oxide  dissolved  more  freely 
than  the  opaque  variety,  whilst  under  another  the  reverse  was  the 

case. 

i.  One  part  of  the  crydallized  oxide  was  frequently  agitated 
during  nine  days,  at  the  ordinary  temperature,  with  twenty  parts  of 
pure  water.  The  resulting  solution  contained  one  part  of  the  oxide 
in  108  parts  of  water. 

j.  An  experiment  similar  to  the  last  and  conducted  at  the  same 
time,  with  one  part  of  the  oxide  and  jive  hundred  parts  of  water, 
yielded  a  solution  which  contained  one  part  of  oxide  in  810  parts 
of  the  menstruum. 

The  experiments  now  cited  serve  to  explain,  at  least  in  a  measure, 
the  discrepant  statements  of  observers  in  regard  to  the  solubility  of 
this  substance.  Furthermore,  it  is  obvious  that  unless  something  is 
known  in  regard  to  the  conditions  under  which  the  oxide  and  liquid 
have  been  brought  in  contact,  it  will  be  impossible  to  state  even 
approximately  how  much  of  the  poison  may  have  been  dissolved, 
even  by  pure  water.  In  general  terms,  if  the  mixture  contained 
one  part  of  the  oxide  to  ten  or  twelve  parts  of  water  and  has 
been  boiled  and  concentrated,  the  liquid  may  hold  in  solution  even 
as  much  as  one-seventh  of  its  weight  of  the  poison ;  whilst,  on  the 
other  hand,  if  there  was  very  large  excess  of  water  and  the  mix- 
ture was  not  heated,  the  liquid  may  not  take  up  more  than  the 
1-1 000th  of  its  \Yeight  of  the  oxide. 

Gmelin  placed  pulverized  opaque  arsenious  oxide  in  various 
proportions  of  water  in  closed  bottles,  and  set  them  aside  in  a  cool 
place  for  eighteen  years,  with  the  following  results.  One  part  of 
the  oxide  in  1000  parts  of  water :  perfect  solution.  One  part  of  the 
oxide  in  100  parts  of  water :  the  solution  contained  one  part  of  oxide 
in  102  parts  of  water.  One  part  of  oxide  in  35  parts  of  water : 
the  solution  contained  one  part  of  the  oxide  in  54  parts  of  water. 
{Hand-book  of  Chemistry,  iv.  257.) 

According  to  most  observers,  the  solubility  of  the  poison  is  more 
or  less  diminished  by  the  presence  of  most  kinds  of  organic  matter. 
In  an  ordinary  decoction  of  coffee,  to  which  during  its  prepara- 
tion white  arsenic  had  been  criminally  added.  Dr.  C.  Mclutire  found 
one  part  of  the  oxide  in  solution  in  thirty-nine  parts  of  the  men- 
struum;  and  by  experiment  he  found  that  one  part  of  the  oxide 


256  ARSENIC. 

might  be  taken  up  by  about  twenty  parts  of  the  decoction.     [Proc. 
Am.  Chem.  Soc,  1878,  56.) 

2.  In  Alcohol. — One  part  of  the  crystallized  oxide,  in  the  state  of 
powder,  was  frequently  agitated  for  two  days  with  twenty  parts  of 
alcohol  of  specific  gravity  0.802  (=  97.5  per  cent.).  The  solution 
thus  obtained  contained  one  part  of  oxide  in  2000  parts  of  the  men- 
struum. In  a  similar  experiment  with  the  most  common  kind  of 
whiskey,  one  part  of  the  oxide  dissolved  in  880  parts  of  the  liquid. 

3.  In  Chloroform. — On  frequently  agitating  powdered  arsenious 
oxide  for  two  days  with  twenty  parts  by  weight  of  pure  chloroform, 
two  hundred  grains  of  the  filtered  liquid  contained  something  less 
than  the  1-lOOOth  of  a  grain  of  the  oxide.  This  experiment  would, 
therefore,  indicate  that  the  oxide  required  more  than  200,000  times 
its  weight  of  chloroform  for  solution. 

Absolute  ether,  under  the  conditions  just  mentioned,  failed  to 
dissolve  a  trace  of  the  poison. 

Arsenious  oxide  is  readily  soluble  in  solutions  of  the  fixed  caustic 
alkalies,  but  it  is  much  less  soluble  in  ammonia.  It  is  also  soluble 
in  hydrochloric  acid,  and  in  certain  of  the  vegetable  acids ;  sulphuric 
acid  dissolves  it  only  in  minute  quantity.  Hot  nitric  acid  oxidizes 
and  dissolves  it  to  arsenic  acid. 

Op  Solid  Arsenious  Oxide. 

1.  If  a  small  quantity  of  solid  arsenious  oxide  be  thrown  on  a 
piece  of  ignited  charcoal  or  heated  on  a  charcoal  support  in  the  re- 
ducing blow-pipe  flame,  it  is  dissipated  in  the  form  of  white  fumes 
and  emits  a  garlic-like  odor.  In  this  operation  the  arsenious  oxide 
first  gives  up  its  oxygen  to  the  carbon,  forming  carbon  dioxide  gas ; 
the  metallic  arsenic  thus  set  free  is  then  reoxidized  by  the  air  into 
arsenious  oxide,  which  is  evolved  and  gives  rise  to  white  fumes. 
The  alliaceous  odor  emitted  is  due  to  the  reoxidation  of  the  metal, 
and  is  evolved  only  when  the  metal  itself  is  being  oxidized.  It  was 
formerly  supposed  that  this  odor  was  peculiar  to  arsenic,  but  it  is 
now  known  that  there  are  several  other  substances  which  evolve  a 
similar  odor. 

2.  When  heated  in  a  reduction-tube,  arsenious  oxide  volatilizes 
without  fusing  and  recondenses  in  the  cooler  portion  of  the  tube,  in 
the  form  of  minute,  octahedral  crystals.  Under  the  microscope,  this 
sublimate  is  quite  peculiar,  and  the  crystals  present  the  appearances 


UlODUCriON    TKST.  257 

illiistratod  in  Plate  IV.,  i\\i;.  5.  When  only  a  very  niimilo  (jtiantity 
of  till*  poison  is  tlm.s  snhlinieil,  the  erystals  are  exceedingly  small, 
but  still  })erfectly  characteristic.  Under  an  amplification  of  one  hun- 
dred dianu'ters,  the  angular  iiatui-e  of  a  crystal  that  does  not  ex- 
ceed the  l-8000th  of  an  inch  in  diameter  may  be  readily  recognized  ; 
and  with  a  power  of  two  hundred  and  fifty,  crystals  measuring  only 
tlie  1-1 5,000th  of  an  inch  in  size  may  be  satisfactorily  determined. 
If  suflicient  sublimate  be  obtained,  the  portion  of  the  tube  containing 
it  may  be  boiled  in  a  small  quantity  of  pure  water,  and  the  solution 
thus  obtained,  after  concentration  if  necessary,  examined  by  the  liquid 
tests  mentioned  hereafter. 

In  applying  this  test  to  only  a  minute  quantity  of  arsenious  oxide, 
the  bore  of  the  reduction-tube  should  not  exceed  the  1-1 6th  of  an 
inch  in  diameter.  Or,  after  placing  the  oxide  in  a  tube  of  this  kind 
having  thin  walls,  the  tube  may  be  carefully  heated  at  a  little  distance 
above  the  point  occupied  by  the  oxide,  in  a  small  blow-pipe  flame, 
and  drawn  out  into  a  capillary  neck;  the  oxide  is  then  sublimed  into 
the  contracted  portion  of  the  tube.  By  this  method  the  least  visible 
quantity  of  the  poison  will  yield  a  very  satisfactory  sublimate;  at  the 
same  time,  this  method  permits  the  application  of  the  higher  powers 
of  the  microscope  for  the  examination" of  the  sublimate. 

Prof.  Guy  recommends  [Cheni.  News,  i.  200)  to  heat  the  arsenious 
oxide  in  a  perfectly  dry  tube  of  small  diameter  and  about  three- 
quarters  of  an  inch  in  length  and  having  its  mouth  covered  with  a 
warm  slide  or  disk  of  glass.  The  crystals  are  deposited  partly  on 
the  sides  of  the  tube,  but  chiefly  on  the  glass  cover.  This  method 
oifers  the  advantage  of  having  the  deposit  upon  a  flat  surface  for 
examination  by  the  microscope;  in  point  of  delicacy,  however,  it  is 
very  far  inferior  to  the  preceding  method. 

In  applying  this  sublimation-test  to  a  suspected  substance,  it 
must  be  borne  in  mind  that  there  are  other  white  powders  besides 
arsenious  oxide,  as  salts  of  ammonium,  oxalic  acid,  and  corrosive 
sublimate,  which  when  heated  in  a  reduction-tube  may  yield  a  crys- 
talline sublimate.  But  most,  if  not  all,  of  these  fallacious  substances 
melt  before  volatilizing,  and  none  of  them  condense  in  the  form  of 
octahedral  crystals. 

3.  Reduction   Test. 

a.  If  a  small  quantity  of  arsenious  oxide  be  placed  in  the  closed 
end  of  a  narrow  reduction-tube,  or  in  the  end  of  a  tube  drawn  out  in 

17 


258  ARSENIC. 

the  form  shown  in  Fig.  5,  and  a  wedge  of  recently  ignited  char- 
coal, h,  be  placed  in  the  tube  a  little  distance  above  the  arsenical 
fragment  or  powder,  on  heating  the  charcoal  to  redness  by  the  flame 
of  a  spirit-lamp  and  then  slowly  erecting  the  outer  end  of  the  tube 
so  that  the  flame  may  still  heat  the  charcoal  and  at  the  same  time 
volatilize  the  arsenious  oxide,  the  latter  will  be  deoxidized  in  its 

passage  over  the  ignited  charcoal  and  yield 
Fig.  5.  a  sublimate,  c,  of  metallic  arsenic.     This 

■^^--?—  ■  -«Si^=ssi=^^=(ii     reduction  may  also  be  eifected  by  mixing 

O'     0       o  ... 

m  V,  ^   iv.      J    .•      .        ■         the  arsenious  oxide  with   a  perfectly  dry 

Tube  for  the  reduction  of  arsenious  '  j  J 

oxide  by  charcoal.  One-third  nat-  mixture  of  powdcrcd  charcoal  and  sodium 
""^^  ^^^^'  carbonate,    and    heating    the   whole   in    a 

plain  or  bulbed  reduction-tube. 

The  sublimate  thus  obtained  usually  consists  of  two  well-defined 
parts,  the  lower  of  which  has  a  bright  mirror  appearance  resembling 
polished  steel;  while  the  upper  has  a  darker  color,  is  destitute  of 
lustre,  and  is  gradually  lost  in  a  light-gray  mist.  The  inner  surface 
of  the  sublimate,  especially  of  the  lower  ring,  presents  a  bright  crys- 
talline appearance.  Sometimes  the  upper  portion  of  the  sublimate, 
wdien  very  thin,  has  a  brownish  color.  So,  also,  sometimes  its  upper 
margin  contains  crystals  of  arsenious  oxide. 

If  the  closed  end  of  the  tube  be  removed  and  the  sublimate  then 
heated,  it  is  readily  volatilized  and  oxidized  into  arsenious  oxide, 
which  condenses  in  octahedral  crystals.  The  metallic,  sublimate  is 
soluble  in  a  solution  of  either  sodium  or  calcium  hypochlorite.  This 
confirmatory  test  may  be  applied  by  removing  the  lower  end  of  the 
tube,  and  then  immersing  the  latter  in  a  small  quantity  of  the  sodium 
solution  ;  or,  a  few  drops  of  the  solution  may  be  drawn  into  the  tube, 
after  the  removal  of  its  closed  end,  by  suction  with  the  mouth.  The 
upper  portion  of  the  sublimate  readily  disappears  when  moistened 
with  this  liquid,  but  the  lower  part  requires  some  little  time  for 
solution  ;  sometimes  the  deposit  becomes  detached  and  drops  out  of 
the  tube  in  the  form  of  a  metallic  ring.  The  arsenical  nature  of  the 
sublimate  may  also  be  shown  by  dissolving  it  in  a  few  drops  of  warm 
nitric  acid,  evaporating  the  solution  to  dryness  by  a  moderate  heat, 
and  touching  the  residue  with  a  drop  or  two  of  a  strong  solution 
of  silver  nitrate,  when  it  will  assume  a  brick-red  color,  due  to  the 
formation  of  silver  arsenate. 

6.  One  of  the  best  methods  yet  proposed  for  the  reduction   of 


REDUCTION    TEST.  259 

solid  urseiiious  oxide,  and  one  wliioli  is  equally  applicable  for  arsenites 
and  llio  siil|)lii(les  of  arsenic,  is  hy  means  of  a  pcrfcdhj  dry  mixture 
of  about  ('(jnal  j)arts  of  .-lodium  carbonate  and  poldHHium  ci/anlde.  A 
small  portion  of  the  arsenical  compound  is  introduced  into  tlu;  bulb 
of  a  tube  of  the  form  shown  in  Fio;.  6,  A,  or  of  the  form  i>  as  iirst 
proposed  by  Berzelius,  and  covered  with  several  times  its  volume  of 
the  above  mixture.  A  gentle  heat  is  then 
applied,  first  to  the  neck  of  the  tube  and 
afterward  to  the  bulb;  if  in  this  opera- 
tion any  moisture  condenses  within  the 
tube,  it  should  be  carefully  removed.  On 
now  strongly  heating  the  mixture,  the 
compounil  under  examination  will  be  re- 
duced and  yield  a  metallic  sublimate  at 


about  the  ]H)int  6.     This  reaction  is  ex-       oc- 

1  1    1*^    A„       ^^„^„:„11„     ,.A.^^      ■.^^,,       Tubes  for  the  reduction  of  araenious 

tremely   delicate,    especially    wlien    per-  ^^.^^ 

formed  in  a  Berzelius-tube. 

When  only  a  very  minute  quantity  of  the  arsenical  compound 
is  to  be  reduced,  it  may  be  placed  in  the  closed  end  of  an  ordinary 
reduction-tube,  covered  by  the  reducing  mixture,  and  the  tube  then 
heated  at  a  little  distance  above  the  mixture  in  a  blow-pipe  flame, 
and  drawn  out  into  a  contracted  neck,  as  represented  in  Fig.  6,  C. 
After  the  neck  of  the  tube  has  cooled,  the  arsenical  mixture  is  heated 
in  the  manner  above  described.  A  mixture  containing  only  the 
1-1 000th  of  a  grain  of  arsenious  oxide,  when  treated  after  this 
method  in  a  tube  having  its  neck  contracted  to  about  the  1— 20th 
of  an  inch  in  diameter,  will  yield  a  very  satisfactory  metallic  subli- 
mate, which  u})on  resubliraation  farther  up  the  neck  of  the  tube  will 
furnish  several  hundred  crystals  of  arsenious  oxide,  many  of  them 
measuring  the  1-lOOOth  of  an  inch  in  diameter.  Compounds  of 
antimonyyield  no  sublimate  whatever  when  heated  with  the  reducing 
mixture. 

c.  As  a  reducing  agent  for  arsenious  oxide,  arsenites,  and  the 
sulphides  of  arsenic,  as  well  as  for  other  metallic  compounds.  Dr. 
E.  Davy,  of  Dublin,  has  recommended  potassium  ferrocyanide,  or 
yellow  prussiate  of  potash,  previously  dried  at  a  temperature  of 
i00°  C.  (212°  F.).  {Chemical  News,  iii.  288.)  This  salt  has  an 
advantage  over  potassium  cyanide,  in  that  it  does  not  readily  absorb 
moisture  from  the  atmosphere.     The  arsenical  compound  is  mixed 


260  AESENIC. 

with  about  six  or  eight  times  its  volume  of  the  dried  salt,  and  the 
mixture  fused  in  one  or  other  of  the  reduction-tubes  already  de- 
scribed. The  mixture  blackens  before  fusing.  In  point  of  delicacy 
the  reaction  of  this  reducing  agent  is  quite  equal  to  that  of  potas- 
sium cyanide. 

Fallacies. — \yhen,  by  either  of  the  above  methods  of  reduction, 
a  metallic  sublimate  having  the  physical  and  chemical  properties 
described  is  obtained,  there  is  no  doubt  whatever  of  the  presence  of 
arsenic.  Compounds  of  mereury,  cadmium,  tellurium,  and  selenium 
may  under  similar  circumstances  yield  sublimates.  These,  however, 
may  be  readily  distinguished  from  the  arsenical  sublimate,  even  by 
the  naked  eye ;  under  the  microscope  they  would  be  found  to  con- 
sist of  globules  or  drops.  Moreover,  neither  of  these  sublimates 
when  revolatilized  will,  like  arsenic,  furnish  octahedral  crystals;  nor 
are  tliey  soluble  in  a  solution  of  sodium  hypochlorite.  Xeither  will 
they,  when  dissolved  in  hot  nitric  acid  and  the  solution  evaporated 
to  dryness,  leave  a  residue  which  assumes  a  brick-red  color  when 
moistened  with  a  solution  of  silver  nitrate. 

It  has  also  been  stated  that  a  crust  of  charcoal  or  the  employment 
of  a  reduction-tube  containing  lead  might  lead  to  error;  but  it  is  diffi- 
cult to  conceive  how  either  of  these  results  could  be  mistaken  for  an 
arsenical  sublimate  by  any  one  at  all  conversant  with  the  physical 
appearances  of  the  latter. 

Solutions  of  Aesexious  Oxide. — xIrsexious  Acid. 

Pure  aqueous  solutions  of  arsenious  oxide  have  only  a  feeble  acid 
reaction.  This  reaction  is  common  to  both  varieties  of  the  oxide, 
and  is  still  manifest  in  a  solution  containing  only  the  1-lOOOth  of 
its  weight  of  the  poison.  On  allowing  a  drop  of  a  solution  of  this 
kind  to  evaporate  spontaneously  to  dryness,  for  convenience  on  a 
glass  slide,  the  oxide  will  be  left  chiefly  in  the  form  of  white,  oc- 
tahedral crystals,  wdiich  are  readily  dissipated  by  heat.  The  residue 
thus  obtained  from  the  1— 100th  of  a  grain  of  the  acid  will  usually 
contain  many  crystals  that  measure  the  1— 1000th  of  an  inch  in 
diameter.  Equally  satisfactory  results  may  be  obtained  from  the 
1-lOOOth  of  a  grain  of  the  oxide,  but  the  crystals  are  usually  quite 
small.  From  the  1-10, 000th  of  a  grain  of  the  oxide  the  crystals  are 
very  minute,  but  under  the  higher  powers  of  the  microscope  their 
true  nature  may  be  very  satisfactorily  determined.     The  production 


AMMONIO   SILVER    NITRATE   TEST.  261 

of  these  octaliedrul  crystals,  completely  vaporizable  by  heat,  is  pe- 
culiar to  arseiiious  oxide.  The  dry  residue  thus  obtained  may,  of 
<'uurse,  be  examined  by  any  of  the  tests  ah'cady  mentioned  for  the 
poison  in  its  solid  state. 

In  the  followin*;-  investitrations  in  regard  to  tiie  behavior  of  solu- 
tions ot'arsenious  oxide,  solutions  of  the  |)urc  crystallized  oxide  were 
employed.  The  fractions  indicate  the  amount  of  anhydrous  oxide 
present  in  one  grain  of  the  solution.  The  results,  unless  otherwise 
stated,  refer  to  the  reactions  of  one  grain  of  the  solution. 

1 .  Ammonio  Silver  Nitrate. 

This  reagent  is  prepared  by  cautiously  adding  a  dilute  solution 
of  ammonia  to  a  solution  of  silver  nitrate,  until  the  merest  trace  of 
the  precipitate  first  produced  remains  undissolved.  It  is  important 
that  the  proper  quantity  of  ammonia  be  added  :  since  if  there  is 
deficiency,  the  reagent  will  also  produce  yellow  precipitates  with  solu- 
tions of  the  alkali  phosphates  and  silicates;  whilst,  on  the  other  hand, 
if  there  is  excess,  it  occasions  no  preci])itate,  or  only  a  partial  one, 
with  arsenious  acid.  The  reagent  should  always  be  freshly  prej)ared. 
Nitrate  of  silver  alone  produces  at  most  only  a  slight  turbidity  in 
solutions  of  free  arsenious  acid;  but  with  neutral  arsenites  it  behaves 
in  the  same  manner  as  the  ammonio-nitrate  with  the -free  acid.  This 
test  was  first  proposed,  in  1789,  by  Mr.  Hume,  of  London. 

Ammonio  silver  nitrate  throws  down  from  aqueous  solutions  of 
arsenious  acid  a  bright  yellow  precipitate  of  tribasic  silver  arsenite, 
AgjAsOj,  the  reaction  being,  j)erhaps,  2H3ASO3-I- GAgXHjNOg^^ 
2Ag3As03-|-  GNH^NOg.  According  to  some  observers,  however,  the 
reagent  has  the  composition  AgXH2,NH^X03,  and  the  reaction  is 
2H3As03-f  6AgXH2,XH,X03=  2Ag3As03  +  6XH,X03  +  6XH3. 

The  precipitate  is  readily  soluble,  to  a  colorless  solution,  in  am- 
monia and  in  nitric  and  acetic  acids,  sparingly  soluble  in  ammonium 
nitrate,  and  insoluble  in  the  fixed  caustic  alkalies.    After  a  little  time 
the  precipitate  becomes  more  or  less  crystalline,  and  is  then  insoluble 
in  ammonia  and  in  acetic  acid.     Hydrochloric  acid  decomposes  the 
precipitate  with  the  formation  of  white  insoluble  silver  chloride. 
1.  YoiF  grain  of  arsenious  oxide,  in  one  grain  of  water,  yields  with  the 
reagent  a  copious,  bright  yellow,  amorphous  precipitate,  which 
after  a  little  time  becomes  converted  into  yellowish-brown  crys- 
tals, of  the  forms  illustrated  in  Plate  IV.,  fig.  6.     The  crystals 


262  ARSENIC. 

closely  adhere  to  the  glass  upon  which  they  have  formed,  and 
are  insoluble  in  large  excess  of  ammonia  and  of  acetic  acid, 

2.  YFoo"  gi'ai"  yields  a  rather  copious  precipitate,  which  partly  becomes 

crystalline. 

3.  5-0V0"  gi^aiii  •  a  quite  good  deposit,  which  remains  amorphous. 

4.  YF-ToT  grain :  an  immediate  yellowish  turbidity,  and  in  a  little 

time  small  yellow  flakes. 

5.  -g-g.-o-oo"  gi'ain  :  after  a  little  time  the  mixture  becomes  very  dis- 

tinctly turbid,  and  when  viewed  over  a  white  surface,  as  white 
paper,  presents  a  slight  yellow  tint.     Ten  grains  of  the  solution 
yield  an  immediate  yellowish  turbidity,  and  after  a  little  time 
small  flakes  having  a  decided  yellow  color.     When  examined  in 
large  quantity,  solutions  even  much  more  dilute  than  this  will 
yield  very  distinct  reactions. 
If  the  silver  arsenite  thrown  down  by  this  reagent  be  decomposed 
by  slight  excess  of  hydrochloric  acid  and  the  silver  chloride  separated 
by  a  filter,  the  clear  acid  filtrate  will  yield  with  sulphuretted  hydro- 
gen gas  a  bright  yellow  precipitate  of  arsenious  sulphide,  having  the 
properties  to  be  pointed  out  hereafter.     When  the  silver  arsenite  is 
washed,  thoroughly  dried,  and  heated  in  a  reduction-tube,  it  under- 
goes decomposition  with  the  production  of  a  sublimate  of  octahedral 
crystals  of  arsenious  oxide ;  when  heated  in  a  similar  manner  with 
a  reducing  agent,  such  as  potassium  ferrocyanide,  it  yields  a  subli- 
mate of  metallic  arsenic.     By  either  of  these  methods  the  arsenical 
nature  of  very  minute  quantities  of  the  silver  precipitate  may  be  fully 
established. 

Fallacies. — Ammonio  silver  nitrate  also  produces  in  solutions  of 
free  phosphoric  acid  a  yellow,  amorphous  precipitate,  which  is  readily 
soluble  in  nitric  acid  and  in  ammonia  ;  this  precipitate  always  remains 
amorphous.  So,  also,  the  reagent  produces  a  somewhat  similar  pre- 
cipitate in  solutions  of  free  vanadic  acid;  but  these  solutions,  unlike 
those  of  arsenious  acid,  have  a  yellow  color.  Both  free  phosphoric 
and  vanadic  acids,  especially  the  latter,  are  extremely"  rare,  and  there- 
fore not  likely  to  be  met  with  in  medico-legal  investigations.  The 
properly  prepared  reagent  fails  to  produce  a  precipitate  in  solutions 
of  the  salts  of  either  of  these  acids.  Again,  solutions  of  the  alkali 
iodides  and  bromides  yield  with  the  reagent  yellowish  precipitates ; 
but  these  precipitates  are  insoluble  in  dilute  nitric  acid,  and  only 
slightly  soluble  in  caustic  ammonia. 


AMMONIO   (X)PPER   SULPHATE   TEST.  263 

It  need  liiinlly  Ix'  rcmarketl  that  iicitlicr  of"  the  al)ove  precipi- 
tates, when  dried  and  heated  either  ah)iie  or  with  a  re<hieinf;  'if^ciit, 
in  a  re(hiotion-tnbe,  will  yield  an  octahedral  or  metallic  sublimate. 
Neither  ot"  the  above  acids  is  a  source  of  fallacy  to  any  of"  the  other 
tests  for  arsenic. 

Should  arseuious  acid  and  a  cldoride,  as  common  salt,  occur  in  the 
same  sohition,  the  latter  compound  will  yielil  with  the  silver  reagent 
a  white  precipitate  of  silver  chloride,  which  will  obscure  the  arsenical 
reaction.  From  a  mixture  of  this  kind  the  chlorine  may  be  removed 
by  treating  the  solution,  after  the  addition  of  a  drop  of  nitric  acid, 
with  slight  excess  of  pure  silver  nitrate,  and  filtering.  On  now 
exactly  neutralizing  the  filtrate  with  ammonia,  the  yellow  silver 
arsenite  will  separate. 

Since  ammonio  silver  nitrate  is  decomposed  with  the  production 
of  a  precipitate,  even  in  the  absence  of  arsenious  acid,  by  most  organic 
solutions,  the  test  is  not  applicable  to  mixtures  of  this  kind.  • 

2.  Ammonio  Copper  Sulphate. 

This  reagent  is  prepared  by  cautiously  adding  ammonia  to  a 
somewhat  dilute  solution  of  copper  sulphate,  until  the  precipitate 
first  produced  is  very  nearly  all  redissolved ;  the  clear  liquid  is  then 
decanted.  The  reagent  produces  in  solutions  of  arsenious  oxide  a 
green,  amorphous  precipitate  of  copper  arsenite  (CuHAsOg),  known 
also  as  Scheek's  green,  the  reaction  being,  perhaps,  2H3As03-r 
2CuHA(^^H3)2,(XHj2SO,=2CuHAs03+2(NH,)2SO,4-4XH„HO. 
Chemists,  however,  are  by  no  means  fully  agreed  as  to  the  exact 
composition  of  Scheele's  green. 

The  precipitate  is  nearly  insoluble  even  in  large  excess  of  the 
precipitant,  but  readily  soluble  in  ammonia  and  in  free  acids.  From 
very  dilute  solutions  of  the  poison  the  precipitate  does  not  appear  of 
its  characteristic  color  until  the  mixture  has  stood  for  some  time. 
The  same  precipitate  is  thrown  down  from  solutions  of  neutral 
arsenites  by  copper  sulphate  alone. 

1.  YWH  grain  of  arsenious  oxide,  in  one  grain  of  water,  yields  a  very 

copious,  yellowish-green  precipitate,  which  when  washed  acquires 
a  bright  green  color. 

2.  YWoo  gi'^hi :  a  rather  copious,  green  deposit. 

3.  3-oV(r  grain  :  a  good,  bluish-green  precipitate,  which  after  a  little 

time  assumes  a  distinct  green  color,  the  blue  tint  disappeai'ing. 


264  ARSENIC. 

The  true  color  of  these  precipitates  is  best  seen  when  examined 

over  a  white  surface. 
4.  Yo'.Wo'  g^'sio  •  a°  immediate  bluisli  floccUlent  precipitate,  which 

after  a  little  time  acquires  a  light  green  color.     The  precipitate 

from  ten  grains  of  the  solution  soon  acquires  a  fine  green  color. 
Ten  grains  of  a  l-25,000th  solution  of  the  oxide  yield  an  im- 
mediate blue  precipitate,  which   in  a    little  time   acquires  a  light 
green  hue. 

Fallacies. — There  is  no  other  metallic  substance,  besides  arsenic, 
known  that  yields  with  this  reagent  a  similar  precipitate.  But  various 
organic  substances  yield  with  the  reagent  a  precipitate  having  in  some 
instances  a  color  somewhat  resembling  that  of  the  arsenite  of  copper. 
So  far,  therefore,  as  the  mere  production  of  a  greenish  precipitate  is 
concerned,  no  reliance  whatever  could  be  placed  in  the  tests  when 
applied  to  organic  solutions. 

The  arsenical  nature  of  copper  arsenite  may  be  shown  by  heating 
the  dried  precipitate,  either  alone  or  with  a  reducing  agent,  in  a  reduc- 
tion-tube, when  it  will  yield  a  sublimate  of  octahedral  crystals  of 
arsenious  oxide  or  of  metallic  arsenic,  as  the  case  may  be.  When 
dissolved  in  hydrochloric  acid  and  boiled  with  a  slip  of  bright  copper- 
foil,  arsenite  of  copper  is  decomposed,  with  the  deposition  of  metallic 
arsenic  upon  the  copper-foil :  the  true  nature  of  this  deposit  may  be 
shown  in  the  manner  to  be  described  hereafter,  under  the  consider- 
ation of  Reinsch's  test.  If  the  hydrochloric  acid  solution  of  the 
arsenite  be  treated  with  sulphuretted  hydrogen  gas,  it  will  yield  a 
brown  or  dark-brown  precipitate,  consisting  of  a  mixture  of  the  sul- 
phides of  arsenic  and  copper.  If  this  precipitate  be  collected  on  a 
filter,  washed,  and  then  digested  with  ammonia,  the  latter  will  dis- 
solve the  arsenious  sulphide,  while  the  copper  sulphide  will  remain 
undissolved.  On  now  filtering  the  ammoniacal  solution  and  care- 
fully neutralizing  it  with  hydrochloric  acid,  the  arsenious  sulphide 
will  separate  in  the  form  of  a  bright  yellow  precipitate. 

3.  Sulphuretted  Hydrogen. 

Sulphuretted  hydrogen  gas,  or  JHydrosulphuric  add,  throws  down 
from  solutions  of  arsenious  acid,  previously  acidulated  with  hydro- 
chloric acid,  a  bright  yellow,  amorphous  precipitate  of  arsenious 
sulphide,  or  sesquisulphide  of  arsenic,  AsgSg,  known  also  as  Orpi- 
ment,  the  reaction  being  'iHgAsOg  -f-  3H2S= AsgSg  -f-  GHgO.    For  the 


SULPHURETTED    HYDROGEN   TEST.  2f)5 

application  of  this  test,  a  siiiall  (|iiaiitity  of  iron  snlpliidc  may  l>e 
introilueetl  info  an  ordinary  gas-evolution  flask  and  covered  with 
pure  water;  the  mouth  of  the  flask  is  then  (;loscd  by  a  cork  having 
two  perforations,  one  of  which  carries  a  Innnel-tnbe,  and  the  other 
an  cxit-lnbe  bent  twice  at  right  angles.  Sufficient  sulphuric  acid  is 
then  added  to  the  contents  of  the  flask,  by  means  of  the  funnel-tube, 
to  cause  the  evolution  of  a  moderate  stream  of  sulphuretted  hydrogen  ; 
this  is  conducted  into  the  acidulated  arsenical  solution,  contained  in 
a  test-tube  or  any  convenient  vessel.  When  the 
quantity  of  material  to  be  examined  is  very  small, 
the  apparatus  illustrated  in  Fig.  7  may  be  era- 
ployed.  From  very  dilute  solutions  the  precipi- 
tate does  not  separate  until  the  excess  of  the 
reagent  added  is  expelled  by  a  gentle  heat  or  by 
exposure  to  the  air.  In  all  cases  a  gentle  heat 
hastens  the  complete  separation  of  the  precipitate. 
Arsenious  sulphide  is  insoluble  in  cold  hydro- 
chloric acid,  and    only   very  slightly  soluble  in     Apparatus  for  detecting 

,,.,.  I'll  ••  -11  arsenic    by  sulpburet- 

tlie  boiling  concentrated  acid;  hot  nitric  acid  de-       ted  hydrogen, 
composes  and  dissolves  it  to  arsenic  acid.    It  is 
readily  soluble,  to  a  colorless  solution,  in  the  caustic  alkalies,  and  in 
the  alkali  sulphides  and  carbonates. 

When  ten  grains  of  a  pure  aqueous  solution  of  arsenious  oxide 
are  placed  in  a  small  test-tube,  acidulated  with  two  drops  of  hydro- 
chloric acid,  and  treated  with  a  slow  stream  of  the  washed  sulphu- 
retted gas,  the  following  results  are  obtained. 

1.  1-lOOth  solution  (1-lOtli  grain  of  arsenious  oxide)  yields  a  very 

copious,  bright  yellow  precipitate,  which  remains  amorphous. 

2.  1-lOOOth   solution  :    an  immediate  precipitate,  which  very  soon 

becomes  quite  copious. 

3.  l-10,000th    solution  :    an    immediate  yellow   turbidity  ;    if  the 

mixture,  after  being  saturated  with  the  gas,  be  allowed  to  stand 
at  the  ordinary  temperature  for  several  minutes,  quite  good 
yellow  flakes  appear,  and  these  after  a  time  fall  to  a  very  good 
deposit.  If  the  mixture  be  heated,  the  precipitate  separates 
almost  immediately. 

4.  l-25,000th  solution  :  very  soon  a  yellow  turbidity ;  after  stand- 

ing about  ten  minutes  yellow  flakes  are  just  perceptible ;  and 
after  a  few  hours  there  is  a  quite  satisfactory  depasit.     If  after 


266  ARSENIC. 

the  introduction  of  the  gas  the  mixture  be  heated,  the  deposit 
appears  within  a  very  few  ruinutes. 

5.  1— 50,000th  solution:  after  a  little  time  a  perceptible  yellowish 

turbidity;  in  about  an  hour  distinct  flakes  appear  suspended  in 
the  liquid,  but  their  color  is  not  satisfactory ;  after  a  few  hours 
they  assume  a  distinct  yellow  hue,  but  still  remain  suspended 
in  the  fluid,  from  which,  however,  they  almost  immediately 
separate  on  the  application  of  heat. 

6.  l-100,000th  solution :  after  a  few  minutes  the  mixture  presents 

a  perceptible  cloudiness ;  after  several  minutes  a  distinct  tur- 
bidity and  a  just  perceptible  yellow  tint ;  after  a  few  hours 
distinct  flakes  appear,  but  their  true  color  is  not  apparent;  after 
thirty-six  hours  there  is  a  quite  distinct  yellow  deposit.      One 
hundred  grciins  of  the  solution   yield  in  a  little  time  a  very 
perceptible  yellowish   turbidity;   after  a  few  hours  a   decided 
yellow  deposit ;  in  twenty-four  hours  the  deposit  is  about  the 
same  as  that  from  ten  grains  of  a  1-1 0,000th  solution  which 
has  stood  the  same  length  of  time. 
When  normal  solutions  of  the  acid  are  treated  with  the  reagent, 
they  also  yield  arsenious  sulphide ;  but  under  these  conditions  the 
arsenical  sulphide,  except  when  from  concentrated  solutions,  entirely 
remains  in  solution,  imparting  a  yellow  color  to  the  liquid.      Ten 
grains  of  a  1-lOOth  solution  of  this  kind  yield  after  a  little  time  a 
quite  good  yellow  precipitate ;  but  the  same  quantity  of  a  1— 1000th 
solution  yields  only  an  intensely  yellow  liquid;  a  1-25, 000th  solution 
yields  a  quite  distinct  yellow  coloration  ;  and  a  1-50, 000th  solution, 
after  a   little  time,  acquires  a  perceptible  yellow  tint.       Alkaline 
solutions  of  the  acid,  even  when  highly  concentrated,  altogether  fail 
to  yield  a  precipitate  when  treated  with  the  reagent. 

The  limit  of  the  visible  reaction  of  this  test,  when  applied  to 
acidulated  solutions  of  the  poison,  has  been  variously  stated  by 
different  observers.  Thus,  Lassaigne  placed  it,  for  solutions  acid- 
ulated with  hydrochloric  acid,  at  one  part  of  arsenious  oxide  in 
80,000  parts  of  liquid ;  Reiusch,  at  one  part  in  90,000 ;  Brandes, 
one  part  in  160,000;  Devergie,  one  part  in  500,000;  and  Horsley, 
at  one  part  in  1,120,000  parts  of  fluid.  Dr.  Taylor  states  that  the 
l-400th  of  a  grain  of  the  poison  in  half  an  ounce  of  water  pro- 
duced a  scarcely  perceptible  yellow  tint.  In  this  case  the  acid  was 
present  in  something  less  than  100,000  parts  of  liquid. 


SULPHURETTED    HYDROGEN    TEST.  267 

As  neither  of  tliese  observei-s,  except  Dr.  Taylor,  states  the 
quantify  of  sohition  operated  upon,  these  discrepancies  are  easily 
reconciled.  The  effect  of  quantity  is  well  illustrated  under  experi- 
ment G,  in  which  ten  grains  and  one  hundred  f/j-ains  respectively  of 
the  same  solution  were  employed.  Here  it  will  be  observe<l  that 
althoiii^h  the  degree  of  dilution  was  the  same,  yet  the  absolute 
quantity  of  arsenic  in  one  case  was  ten  times  greater  than  in  the 
other,  and  the  results  differed  correspondingly.  It  is  obvious  that  a 
similar  difference  would  be  observed  between  different  quantities  of 
any  other  solution,  until  the  degree  of  dilution  equalled  the  solubility 
of  the  arsenious  sulphide,  when  no  quantity,  however  great,  would 
yield  a  precipitate. 

Confirmation  of  the  Precipitate. —  The  arsenical  nature  of  arseni- 
ous sulphide  may  be  established  by  either  of  the  following  methods: 

1.  When  the  hydrochloric  acid  mixture  containing  the  precipi- 
tate is  boiled  with  a  slip  of  bright  copper-foil,  the  sulphide  is  decora- 
posed  with  the  deposition  of  metallic  arsenic  upon  the  copper;  if 
the  coated  copper  be  then  washed,  dried,  and  heated  in  a  reduction- 
tube,  the  metallic  arsenic  is  volatilized  and  yields  a  sublimate  of 
octahedral  crystals  of  arsenious  oxide.  In  this  manner  the  nature 
of  the  precipitate  from  even  less  than  the  1-lOOOth  of  a  grain  of 
the  poison  may  be  fully  established. 

2.  When  arsenious  sulphide  is  dissolved  in  a  few  drojis  of  hot 
nitric  acid,  the  solution  cautiously  evaporated  to  dryness,  and  the  dry 
residue  treated  with  a  few  drops  of  a  strong  solution  of  silver  nitrate, 
it  assumes  a  brick-red  color,  due  to  the  formation  of  silver  arsenate. 

3.  When  washed,  dried,  and  heated  in  a  reduction-tube,  the  ar- 
senical sulphide  readily  fuses  to  an  orange-colored  mass,  then  entirely 
volatilizes,  yielding  a  sublimate,  the  lower  portion  of  which  generally 
has  an  orange-red  color  and  consists  of  microscopic  globules  or  drops  ; 
the  upper  part  of  the  sublimate  has  a  yellow  color,  and  its  upper 
margin  contains  crystals  of  arsenious  oxide.  Small  precipitates  of 
the  sulphide  are  most  readily  recovered,  as  recommended  by  Dever- 
gie,  by  collecting  them  on  a  small  filter,  dissolving  in  ammonia,  and 
evaporating  the  solution  at  a  gentle  heat  to  dryness,  in  a  watch- 
glass,  when  the  sulphide  remains  as  a  yellow  residue. 

4.  When  the  dried  precipitate  is  mixed  with  several  times  its 
volume  of  well-dried  potassium  ferrocyanide,  or  of  a  thoroughly 
dried  mixture  of  one  part  of  potassium  cyanide  and  three  parts  of 


268 


AESENIC. 


sodium  carbonate,  and  heated  in  a  reduction-tube,  it  undergoes  decom- 
position, with  the  production  of  a  sublimate  of  metallic  arsenic.  If 
this  operation  be  performed  in  a  reduction-tube  having  a  narrowly 
contracted  neck,  the  precipitate  from  the  1-lOOOth  of  a  grain  of 
arsenious  oxide  will  yield  very  satisfactory  results.  According  to 
M.  Gautier,  this  method  is  attended  with  loss  of  arsenic,  yielding 
only  twenty-nine  out  of  thirty-six  parts.  {Ann.'d'Hyg.,  Jan.  1876, 
153.) 

For  the  reduction  of  arsenious  sulphide  by  a  mixture  of  potassium 
cyanide  and  sodium  carbonate,  Fresenius  and  Babo  recommend  to 
heat  the  arsenical  mixture  in  an  atmosphere  of  dry  carbon  dioxide, 
commonly  known  as  carbonic  acid  gas.  For  this  purpose  they  era- 
ploy  the  apparatus  illustrated  in  Fig.  8. 


Fig.  8. 


Fresenius  and  Babo's  apparatus  for  the  reduction  of  arsenious  sulphide. 


The  flask  A  is  charged  with  a  mixture  of  water  and  lumps  of 
solid  marble,  and  sufficient  hydrochloric  acid  added,  through  the 
funnel-tube  a,  to  evolve  a  moderate  stream  of  the  gas;  this  is  con- 
ducted by  means  of  the  tube  b  into  strong  sulphuric  acid  contained 
in  the  flask  B,  where  it  is  thoroughly  dried ;  the  tube  c  conducts 
the  dried  gas  into  the  reduction-tube  C,  in  which  is  placed  the  arsen- 
ical mixture  d.  When  the  apparatus  is  filled  with  the  gas,  the  tube 
C  is  heated  in  its  whole  length  very  gently  until  the  contained  mix- 
ture is  quite  dry  ;  when  every  trace  of  moisture  is  expelled,  and  the 
stream  of  gas  has  become  so  slow  that  the  single  bubbles  pass  through 


FALLACIES   OF   THE   8ULPHUU   TEST.  269 

till'  siilpliiiric  :i('i(i  in  J>  at  intervals  of"  alxmt  one  .second,  the  redne- 
tion-tiibe  is  heated  to  redness  at  the  point  e  by  means  of  a  spirit- 
hinip  ;  when  e  is  red-hot,  the  flame  of  another  hunp  is  applied  to  the 
mixtnre,  proceed  in  i;-  from  b  to  e,  until  the  whole  of  the  arsenic  is 
expelled.  Tiie  far  ureater  portion  of  the  volatilized  arsenic  recon- 
denses  at/*  while  a  small  j)ortion  escapes  through  7,  imparting  to  the 
surrounding  air  a  peculiar  garlic-like  odor.  By  slowly  advancing 
the  flame  of  the  second  lam])  up  to  /,  the  whole  of  the  condensed 
arsenic  collects  in  the  narrow  neck  of  the  tube.  The  authors  of 
this  process  state  that  it  will  yield  a  perfectly  distinct  metallic  mirror 
from  the  l-300th  of  a  grain  of  arsenious  sulphide. 

Fallacies. — The  only  metal  besides  arsenic  with  which  sulphu- 
retted hydrogen  produces  a  bright  yellow  precipitate  is  cadmium. 
But,  as  the  suljdiide  of  arsenic  when  precipitated  from  organic  solu- 
tions may  have  only  a  dull  yellow  color,  it  is  important  to  bear  in 
mind  that  certain  other  metallic  sulphides,  either  in  their  pure  state 
or  when  mixed  with  organic  matter,  may  also  present  a  similar  ap- 
pearance. The  only  substances  that  under  any  circumstance  could 
thus  be  confounded  Avith  arsenic  are  cadmium,  selenium,  tin,  and 
antimony.  The  sulphides  of  these  substances  pos.sess  the  following 
properties : 

1.  The  sulphide  of  cadmium  is  thrown  down  by  the  reagent  from 
moderately  acid  solutions  of  the  salts  of  the  metal,  but  strongly 
acidulated  solutions  fail  to  yield  a  precipitate.  The  precipitate  is 
readily  decomposed  and  dissolved  by  hydrochloric  acid;  so,  also, 
unlike  arsenious  sulphide,  it  is  insoluble  in  the  alkalies  and  their  sul- 
phides, and  it  is,  therefore,  produced  in  solutions  containing  a  free 
alkali.  When  boiled  with  copper-foil  in  water  acidulated  with 
hydrochloric  acid,  it  fails  to  produce  a  deposit  upon  the  copper. 
Fused  in  a  reduction-tube  with  a  reducing  agent,  it  yields  a  metallic 
sublimate,  which,  however,  in  its  physical  appearance  is  very  unlike 
the  arsenical  deposit,  and  which  when  resublimed  in  the  open  tube 
fails  to  yield  octahedral  crystals. 

2.  Acidulated  solutions  of  selenioiis  acid  yield  with  sulphuretted 
hydrogen  a  precipitate  of  selenium  sulphide,  which  at  first  has  a 
yellow  color,  but  soon  changes  to  reddish-yellow,  and  finally  .to 
orange-red.  In  dilute  solutions  the  precipitate  may  remain  sus- 
pended for  some  time,  and  ])resent  a  yellow  appearance,  much  like 
the  arsenical  compound ;  but  after  a  time  it  separates  of  its  charac- 


270  AESENIC. 

teristic  color.  The  same  precipitate  separates  from  neutral  and  alka- 
line solutions.  The  precipitate,  like  the  arsenical  sulphide,  is  insolu- 
ble in  hydrochloric  acid,  even  on  the  application  of  heat.  Unlike 
the  arsenical  compound,  however,  it  is  wholly  insoluble  in  ammonia. 
It  also  fails  to  yield  a  metallic  deposit  when  boiled  with  diluted 
hydrochloric  acid  and  copper-foil.  When  fused  with  a  reducing 
agent  in  a  reduction-tube,  it  yields  a  sublimate  which  may  resemble 
somewhat  that  produced  by  arsenic,  but  the  deposit  fails  to  yield 
octahedral  crystals  upon  resublimation. 

3.  Per-combinations  of  tin,  or  stannie  compounds,  yield  with  the 
reagent  from  acidulated  solutions  a  precipitate  of  stannic  sulphide, 
SnSg,  the  color  of  which  in  the  moist  state  somewhat  resembles  that 
of  sulphide  of  arsenic,  but  when  dried  it  has  a  very  dull  yellow 
color.  The  same  precipitate  separates  from  neutral,  but  not  from 
alkaline,  solutions.  The  precipitate  is  slowly  soluble  in  cold  hydro- 
chloric acid,  but  readily  in  the  hot  concentrated  acid.  It  is  very 
sparingly  soluble  in  ammonia,  but  readily  soluble  in  potassium  hy- 
drate. When  boiled  with  water  containing  hydrochloric  acid  and 
a  slip  of  copper-foil,  it  may  impart  to  the  latter  a  slight  stain,  but 
when  the  stained  metal  is  heated  in  a  reduction-tube  it  fails  to  yield 
a  crystalline  sublimate.  The  precipitate  also  fails  to  yield  a  metallic 
sublimate  when  heated  in  a  reduction-tube  with  a  reducing  agent. 

4.  The  sulphides  of  antimony,  as  thrown  down  from  pure  acid- 
ulated solutions  by  sulphuretted  hydrogen,  have  an  orange-red  color; 
the  same  precipitates  are  partially  deposited  in  neutral  and  alkaline 
solutions  of  the  metal.  The  precipitates,  unlike  the  arsenious  sul- 
phide, are  soluble  in  cold  concentrated  hydrochloric  acid,  and  nearly 
wholly  insoluble  in  ammonia;  they  are  readily  soluble  in  potassium 
hydrate.  When  boiled  with  diluted  hydrochloric  acid  and  copper- 
foil,  they  impart  to  the  latter  a  metallic  coating,  which  usually  has  a 
violet  color ;  when  the  coated  copper  is  heated  in  a  reduction-tube,  it 
generally  fails  to  yield  octahedral  crystals.  (See  jpost,  275.)  Nor 
will  the  precipitates  when  heated  in  a  reduction-tube  with  a  reducing 
agent  yield  a  metallic  sublimate. 

As  a  source  of  fallacy  of  the  sulphur  test,  it  has  been  claimed 
that  if  the  iron  sulphide  contains  metallic  iron,  as  is  frequently  the 
case,  and  the  iron  salt  or  the  acid  employed  for  its  decomposition 
is  contaminated  with  arsenic,  the  nascent  hydrogen  evolved  by  the 


REINSCII'S   TEST.  271 

metallic  ii'on  will  convert  llu'  arsenic,  in  part  a(  least,  into  arsenii- 
rettod  liydroi^on,  which  may  cjirry  the  metal  over  into  the  solution 
beinj>;  tested  ibr  arsenic.  This,  liowcver,  is  an  error.  In  repeated 
experiments  with  impure  materials  of  this  kind,  we  have  failed  to 
find  the  least  trace  of  arsenic  evolved  from  the  mixture. 

Thus,  when  a  mixture  of  50  j^rammes  each  of  iron  sulphide  and 
m(>tallic  iron  was  treated  in  a  flask  with  100  c.c.  of  diluted  sul- 
phui-ic'  acid  containing  one  gramme  of  arsenious  oxide,  added  small 
portions  at  a  time,  and  the  washed  evolved  gas  conducted  into  100 
c.c.  of  warmed  nitric  acid  of  sp.  gr.  1.40,  which  readily  decomposes 
both  sulphuretted  hydrogen  and  arsenuretted  hydrogen,  not  a  trace 
of  arsenic  was  found  in  the  nitric  acid  residue,  when  most  carefully 
examined  by  Marsh's  apparatus.  Any  arsenic  present  in  the  material 
employed  for  generating  the  sulphuretted  hydrogen  is  immediately 
converted  into  arsenious  sulphide,  and  remains  as  such  in  the  gener- 
ating flask,  the  sulphide  not  being  decomposed  by  nascent  hydrogen. 

4.  Iteinsch's  Test. 

When  a  solution  of  free  arsenious  acid  or  of  an  arsenite  is 
strongly  acidulated  with  hydrochloric  acid,  and  the  mixture  boiled 
with  bright  metallic  copper,  the  latter  decomposes  the  arsenical  com- 
pound and  receives  a  coating  of  metallic  arsenic.  This  fact  was  first 
observed,  in  1843,  by  Reinsch  ;  but  Dr.  Taylor  was  the  first  to  apply 
it  as  a  test  in  medico-legal  investigations.  The  proportion  of  hydro- 
chloric acid  employed  should  form  about  one-eighth  of  the  volume 
of  the  arsenical  solution;  without  the  addition  of  the  acid  the  metal 
is  not  deposited.  The  copper  may  be  employed  in  the  form  either 
of  fine  wire  or  of  very  thin  foil ;  the  latter,  however,  is  preferable. 
It  is  essential  that  the  copper  have  a  bright  surface:  this  is  readily 
effected  by  means  of  a  fine  file  or  of  sand-paper.  The  color  of  the 
metallic  deposit  will  depend  much  upon  the  thickness  of  the  latter: 
when  quite  thin,  it  presents  a  bluish  or  violet  appearance,  but  when 
comparatively  thick,  it  has  a  steel-like  or  iron-gray  color.  When 
the  metallic  coating  is  very  thick,  continued  boiling  causes  it  to 
separate  from  the  copper,  in  the  form  of  grayish  or  black  scales. 

This  deposit  is  not,  as  was  formerly  supposed,  pure  metallic 
arsenic,  but  a  combination  of  this  metal  and  copper.  M.  Lippert 
maintains  that  it  has  a  constant  composition,  being  a  definite  alloy, 
consisting  of  32  per  cent,  of  arsenic  and  68  per  cent,  of  copper,  its 


272  ARSENIC. 

formula  being  CugAsa.  The  large  proportion  of  copper  contained 
by  the  deposit  adds  very  much  to  the  delicacy  of  the  test.  This 
reaction  will  serve  to  withdraw  the  whole  of  the  arsenic  from  solu- 
tions of  arsenious  acid  and  of  arsenites ;  but  when  the  metal  exists 
in  the  form  of  arsenic  acid,  it  is  deposited  only  from  somewhat 
strong  solutions. 

The  arsenical  nature  of  the  deposit  may  be  shown  in  the  following 
manner :  the  coated  copper,  after  being  carefully  washed  with  pure 
water  and  dried  in  a  water-bath,  is  heated  by  means  of  a  spirit-lamp 
in  a  narrow,  perfectly  dry  and  clean  reduction-tube,  when  the  arsenic 
volatilizes,  and,  becoming  oxidized,  yields  a  sublimate  of  octahedral 
crystals  of  arsenious  oxide.  This  sublimate  usually  forms  within 
from  a  quarter  to  half  an  inch  above  the  point  at  which  the  heat  is 
applied.  When  the  sublimate  is  not  exceedingly  minute,  it  presents 
a  well-defined  ring  of  sparkling  crystals  to  the  naked  eye.  Under 
the  microscope,  these  crystals  present  the  appearances  illustrated  in 
Plate  lY.,  fig.  5.  The  absolute  size  of  the  crystals  will  depend 
somewhat  upon  the  quantity  of  the  metal  present,  as  well  as  upon 
the  diameter  of  the  reduction-tube.  The  portion  of  the  tube  con- 
taining the  sublimate  may  be  separated  with  a  file,  boiled  in  a  very 
small  quantity  of  M'ater,  and  the  solution  examined  by  the  ammonio 
silver  nitrate  or  any  of  the  other  tests  for  arsenious  acid. 

When  one  grain  of  a  pure  aqueous  solution  of  arsenious  oxide  is 
acidulated  with  pure  hydrochloric  acid,  and  the  mixture  heated  in  a 
thin  watch-glass  with  a  small  fragment  of  bright  copper-foil,  it  yields 
the  following  results. 

1.  YoT  g^^i"  of  arsenious  oxide  yields  a  copious,  iron-gray  deposit, 

which  when  heated  in  a  narrow  reduction-tube  furnishes  a  very 
good  sublimate,  consisting  of  innumerable  octahedral  crystals. 

2.  YoVo  g^^i'i  yields  a  good,  steel-like  deposit,  which  when  sublimed 

in  a  reduction -tube  yields  results  similar  to  1,  only  that  the  crys- 
tals are  generally  somewhat  smaller. 

3.  Yo".ToT  E^^^^  '•  ^^  j.soon  as  the  mixture  is  heated  to  the   boiling 

temperature  the  copper  shows  a  distinct  deposit,  which  in  a 
little  time  becomes  quite  satisfactory ;  when  this  is  volatilized 
in  a  very  narrow  reduction-tube,  it  yields  a  sublimate  which  is 
visible  to  the  naked  eye,  and  which  under  the  microscope  is 
very  satisfactory. 
When  deposits  smaller  than  the  one  just  mentioned  are  heated  in 


reinsch's  test.  27  "> 

a  reduction-tiil)e  of  llic  ordinary  foi-in,  even  of  very  narrow  bore, 
the  results  are  not  uniform,  owing  to  the  fact  that  the  sublimate  is 
(listributeil  over  a  comparatively  large  space,  and  part  of  it  seems 
entirely  to  escape  condensation,  at  least  in  the  lower  portion  of  the 
tube.  With  such  deposits,  however,  very  uniform  results  may  be 
obtained  by  the  following  method.  A  thin,  j)erfectly  clean  and  dry 
tube,  of  about  the  1-lOth  of  an  inch  in  diameter,  is  drawn  out  into 
a  capillary  neck  having  an  internal  bore  of  about  the  l-40th  of  an 
inch,  as  illustrated  in  Fig.  9,  A. 
The  coated  copper  is  then  intro-  Fig.  9. 

duced  through  the  wider  por-     j^ 

tion  of  the  tube  to  the  point     '     mi'ii'^ 

c,  and  the  neck  of  the  tube  at  /m-  B 

a  little  distance  above  the  cop-  c  ,^^  ) 

per  is  moistened  with  water  or  1^ 

wrapped  with  wet  cotton.     The  Tubes  for  sublimation  of  arsenic.    Natural  size. 

wide  end  of  the  tube  is  then 

cautiously  fused  shut  by  a  very  small  blow-pipe  flame,  and  the  fusion 
slowly  advanced  to  the  point  occupied  by  the  copper,  as  shown  in  B. 
The  capillary  end  may  now  be  fused  shut.  When  wiped  and  exam- 
ined by  the  microscope,  the  arsenical  sublimate  will  be  found  at  about 
the  point  m,  forming  a  very  narrow  ring  of  octahedral  crystals.  As 
these  tubes  may  readily  be  formed  with  walls  less  than  the  1-1 00th 
of  an  inch  in  thickness,  they  permit  the  application  of  the  higher 
powers  of  the  microscope.  They  may  be  reserved  for  future  ex- 
amination ;  after  a  time,  however,  the  sublimate  deteriorates  some- 
what, and  it  may  even,  if  the  deposit  is  very  small,  wholly  dis- 
appear. 

4.  yg-.^-jjij-  grain  :  when  a  fragment  of  copper-foil  measuring  about 
1-lOth  by  l-20th  inch  is  employed,  and  the  mixture  kept  at  a 
boiling  heat  for  some  time,  with  renewal  of  the  evaporated  fluid 
by  pure  water,  the  copper  acquires  a  decided  steel-like  coating; 
when  this  is  sublimed  in  a  tube  of  the  form  described  above,  it 
yields  to  the  naked  eye  a  visible  mist,  which  under  an  ampli- 
fication of  seventy-five  diameters  is  found  to  consist  of  many 
hundreds  of  well-defined  octahedral  crystals.  In  a  number  of 
instances  over  one  hundred  crystals,  varying  in  size  from  the 
l-2000th  to  the  l-8000th  of  an  inch  in  diameter,  were  counted 
in  a  single  field  of  a  two-thirds  inch  objective,  \vithout  change  of 

18 


274  AESENIC. 

focus;  most  of  the  crystals  measured  about  the  l-4000th  of  an 
iuch  in  diameter, 

5.  -5-0,^-oT  grain,  when  treated  for  some  minutes  as  under  4,  imparts 

to  the  copper  a  distinct  steel-like  tarnish,  which  when  volatilized, 
in  the  manner  described  above,  yields  a  very  satisfactory  micro- 
scopic sublimate.  In  many  instances  over  fifty  crystals,  meas- 
uring from  the  l-3000th  to  the  l-10,000th  of  an  inch  in  diam- 
eter, were  counted  in  a  single  field  of  the  objective.  So  far  as 
the  evidence  of  the  presence  of  octahedral  crystals  is  concerned, 
this  sublimate,  under  the  microscope,  is  as  satisfactory  as  that 
from  the  1-lOOtli  of  a  grain  or  larger  quantity  of  arsenious 
oxide,  the  only  difference  being  in  the  size  and  number  of  the 
crystals. 

6.  yoT/UTo"  gi'ain :  the  copper  receives  a  very  slight  tarnish,  which 

when  volatilized  sometimes  yields  a  satisfactory  crystalline  sub- 
limate; but  frequently  the  crystals  are  so  minute  that  their 
angular  nature  cannot  be  satisfactorily  determined. 

For  the  examination  of  these  sublimates  a  magnifying  power  of 
about  seventy-five  diameters  is  generally  the  most  useful.  Under 
this  amplification,  the  angular  nature  of  a  crystal  measuring  the 
l-5000th  of  an  inch  in  diameter  is  perfectly  distinct  and  satisfactory : 
the  weight  of  such  a  crystal  would  not  exceed  the  1 -200,000,000th  of 
a  grain.  Under  the  same  power,  a  crystal  measuring  the  1— 10,000th 
of  an  inch  appears  only  as  a  distinct  point ;  but  with  a  power  of  one 
hundred  and  fifty,  its  angular  form  may  be  distinctly  recognized : 
its  weight  would  be  less  than  the  1-1, 000,000,000th  of  a  grain.  On 
account  of  the  curvature  of  the  glass  tube,  crystals  but  little  less  in 
size  than  the  last  mentioned  are  not  easily  determined,  even  with  the 
higher  powers  of  the  microscope.  It  is  not,  of  course,  intended  to 
imply  that  quantities  of  the  poison  in  themselves  as  small  as  those  just 
mentioned  could  be  recovered  from  a  solution  and  reproduced  in  the 
crystalline  form  ;  but  only  that  these  crystals  may  thus  be  recognized 
and  identified  when  they  form  separate  portions  of  a  sublimate.  The 
least  quantity  of  the  poison  that  will  furnish  these  crystals,  even  with 
the  greatest  care  and  under  the  most  favorable  circumstances,  accord- 
ing to  the  above  method,  is  about  the  l-50,000th  of  a  grain. 

Various  and  very  discordant  limits  have  been  assigned  to  this 
test  by  different  observers.  However,  as  these  experimentalists  only 
state  the  degree  of  dilution,  without  mentioning  either  the  quantity 


FALLACIES   OF    REINSCIl's   TEST.  276 

of  solution  examined,  tlie  size  of  tlie  copper,  or  the  diameter  of  the 
reduction-tube  employed,  these  discrepancies  are  readily  explained. 

Fallacies. — The  prodiirtion  of  ;i  sublimate  of  octahedral  crystiils 
by  this  test  is  quite  characteristi(;  of  arsenic.  \'ai'ious  other  metals, 
however,  as  antimony,  mercury,  silvei-,  bismuth,  platinum,  palladium, 
and  gold,  are  deposited  upon  cojipcr  under  the  same  conditions  as 
arsenic.  Tin  may  also  impart  a  slight  stxiin  to  the  copper;  so,  also, 
organic  matter,  especially  if  it  contain  sulphur;  and  the  prolonged 
action  of  boiling  hydrochloric  acid  alone  may  produce  a  distinct 
tarnish.  The  antimonial  deposit  has  usually  a  peculiar  violet  color, 
while  the  deposits  from  mercury,  silver,  and  bismuth  have  generally 
a  bright  silvery  appearance,  and  that  from  gold  a  yellow  hue.  Under 
certain  circumstances,  however,  most  of  these  deposits  may  closely 
resemble  that  from  arsenic.  The  platinum  and  palladium  deposits 
present  an  appearance  very  similar  to  that  of  the  arsenical  coating. 

Of  these  various  metallic  deposits,  the  only  ones  which,  when 
heated  in  a  reduction-tube,  will,  like  arsenic,  volatilize  and  yield  a 
sublimate,  are  mercury  and  antimony.  But  the  sublimate  from  mer- 
cury consists  of  opaque  spherical  globules,  which,  when  viewed  under 
incident  light  with  the  microscope,  have  a  bright  silvery  appearance  ; 
and  that  from  antimony  is  usually  either  amorphous  or  at  most  gran- 
ular :  both  these  sublimates,  unlike  that  from  arsenic,  are  insoluble 
in  water. 

We  have  elsewhere  shown  [Amer.  Jour.  Med.  Sci.,  Oct.  1877, 
399)  that  the  antimonial  sublimate  may  contain  octahedral  crystals, 
at  least  when  a  comparatively  large  deposit  is  heated.  But  the 
antimony  deposit  requires  a  much  higher  temperature  than  arsenic 
for  its  vaporization,  and,  being  less  volatile,  the  sublimate  is  very 
near  or  only  slightly  in  advance  of  the  copper  slip.  Moreover, 
under  the  microscope,  any  crystals,  if  present,  will  be  found  in  the 
lower  margin  of  the  deposit  and  mixed  more  or  less  with  amorphous 
or  granular  matter.  Sometimes,  though  rarely,  the  antimony  subli- 
mate contains  crystalline  needles.  In  this  connection  it  should  be 
remembered  that  commercial  tartar  emetic  sometimes  contains  suf- 
ficient arsenic,  as  an  impurity,  to  yield  in  this  manner  a  very  distinct 
sublimate  of  octahedral  crystals  in  advance  of  the  antimonial  deposit. 

A  deposit  of  organic  matter  upon  the  copper  may  also  give  rise 
to  a  sublimate,  but  this  is  amorphous,  and  its  true  nature  is  at  once 
revealed  by  the  microscope.     When  very  complex  organic  mixtures 


276  AESENIC. 

strongly  acidulated  with  hydrochloric  acid  are  boiled  for  some  time 
in  contact  with  metallic  copper,  the  metal  may  present  a  very  dis- 
tinct stain,  and  yield  an  amorphous  sublimate  which  sometimes 
contains  small  acicular  crystals,  consisting  apparently  of  a  compound 
of  copper.  This  sublimate  deposits  very  near  the  copper,  and  is  not 
resublimed  upon  the  further  application  of  heat. 

If  sulphur  in  certain  states  of  combination,  especially  as  sulphu- 
rous aeid  or  an  alkaline  sulphite,  be  present  in  the  liquid,  the  copper 
will  receive  a  deposit  or  coating  very  similar  in  appearance  to  that 
produced  by  arsenic  in  certain  quantity.  After  a  time  the  deposit 
may  become  detached  in  metal-like  flakes,  which  have,  as  we  have 
found,  the  composition  CugS.  When  the  coated  copper  is  heated 
in  a  tube,  a  portion  of  the  sulphur  may  be  volatilized  and  yield  a 
sublimate  of  minute  globules  which  in  certain  respects  may  closely 
resemble  an  arsenical  sublimate,  but  readily  distinguished  from  it  in 
not  being  crystalline.  When,  therefore,  sulphurous  acid  is  employed 
as  a  reducing  agent  in  the  preparation  of  a  liquid  for  testing,  it 
should  be  wholly  expelled  before  the  application  of  this  test. 

Finally,  if  the  copper-foil  or  the  reduction-tube  is  not  perfectly 
dry,  the  moisture  may  condense  in  the  form  of  a  mist-like  deposit 
at  about  the  point  at  which  the  arsenical  sublimate  usually  forms; 
but  the  true  nature  of  this  deposit  also  is  at  once  revealed  by  the 
microscope. 

From  what  has  now  been  stated,  it  is  obvious  that  the  presence 
of  arsenic  is  not  fully  established  until  the  coated  copper  yields  a 
sublimate  of  well-defined  octahedral  crystals.  In  applying  this  con- 
firmatory reaction,  however,  it  should  be  borne  in  mind  that  when 
a  comparatively  large  arsenical  deposit  is  heated  in  a  very  small 
reduction-tube  the  sublimate  may  consist  alone  of  granules,  or  a 
portion  of  the  arsenic  may  even  deposit  in  its  metallic  state.  It 
rarely  happens,  however,  that  at  least  the  upper  margin  of  an  arsen- 
ical sublimate  does  not  contain  the  characteristic  crystals.  Should 
there  be  any  doubt  as  to  the  nature  of  the  sublimate,  the  lower  end 
of  the  tube  may  be  removed  and  the  deposit  resublimed,  when,  if 
consisting  of  arsenic,  it  will  be  converted  into  the  crystalline  form. 
In  all  cases  the  size  of  the  reduction-tube  should  be  in  suitable 
proportion  to  the  quantity  of  deposit  to  be  examined. 

But  even  should  this  test,  when  applied  to  a  suspected  solution, 
vield  an  arsenical  sublimate,  it  of  course  would  not  follow  that  the 


FALLACIES   OF    RKINSCH's   TEST.  277 

poison    was   really  derived    from    tlio  suspected    li(|uid,   unless    the 
analyst  was  perfectly  certain  of  the  purity  of  the  hydrochloric  acid, 
and    in  some  instances  also  of  the  cojjper,  employed.     As  found  in 
commerce,  hydrochloric  acid  may  contain  very  notable  quantities  of 
arsenic.     In  all  cases  a  portion  of  the  sample  of  the  acid  about  to 
be  employed   should  first  be  diluted  with   five  or  six  volumes  of 
water  and  boiled  for  about  ten  minutes  with  a  slip  of  bright  coi)per; 
if  this  fails  to  yield  a  deposit,  the  acid  may  be  considered  free  from 
arsenic.     In  regard  to  the  purity  of  copper,  it  is  now  known,  chiefly 
through  the  researches  of  Dr.   Taylor,  that  this  metal,  as  usually 
employed    in    investigations  of  this    kind,  nearly  always  contains 
traces  of  arsenic.     This  impurity,  however,  could  only  lead  to  error 
when  the  copper  is  acted  upon  and   dissolved   by  the  liquid  with 
which  it  is  boiled;  any  arsenic  thus  dissolved  might  then  deposit 
upon  a  fresh  portion  of  the  copper.     This  objection,  therefore,  has 
no  practical  force,  except  in  cases  in  which  a  very  notable  quantity 
of  the  copper  has  dissolved  and  only  a  very  minute  trace  of  arsenic 
has  been  detected.     When,  in  the  application  of  the  test  to  a  sus- 
pected solution,  the  copper  promptly  receives  an  arsenical  deposit, 
which  after  the  addition  of  successive  slips  of  the  metal  ceases  to 
take  place,  it  is  quite  certain  that  the  poison  is  not-derived  from  the 
copjier. 

For  the  detection  of  traces  of  arsenic  in  copper  we  have  found 
the  following  method,  first  advised  by  F.  Field  [Chem.  Gaz.,  1857, 
313),  exceedingly  delicate.  Ten  grains  of  the  copper  are  dissolved  in 
slight  excess  of  pure,  hot  nitric  acid,  the  solution  diluted  to  about 
three  ounces  of  fluid,  and  ammonia  added  until  the  oxide  of  copper 
is  precipitated,  but  not  redissolved  ;  the  precipitate  is  then  redissolved 
by  the  addition  of  about  twenty-five  grains  of  ammonium  oxalate, 
the  copper  oxalate  thus  produced  precipitated  by  slight  excess  of 
hydrochloric  acid,  and  the  mixture  allowed  to  stand  some  hours. 
The  solution  is  then  filtered,  the  filtrate  saturated  with  sulphurous 
acid  gas,  concentrated  to  a  small  volume,  and  tested  for  arsenic,  . 
either  by  sulphuretted  hydrogen  or  by  a  fresh  piece  of  copper. 

For  this  same  pur])ose  Dr.  Odling  recommends  {Jour.  Chem. 
Soe.,  July,  1863,  248)  to  distil  a  few  grains  of  the  copper,  cut  into 
small  pieces,  with  an  excess  of  pure  hydrochloric  acid  and  ferric 
chloride,  the  distillation  being  carried  to  dryness:  the  dry  residue 
may  be  redistilled  with  a  little  fresh   hydrochloric  acid.     By  this 


*278  AESENIC. 

treatment  the  copper  is  quickly  dissolved,  and  any  arsenic  present 
converted  into  chloride  and  thus  carried  over  with  the  distillate. 
The  distillate  is  tested  for  arsenic  in  the  usual  manner.  Ferric 
chloride,  Dr.  Odling  adds,  may  be  purified  from  arsenic  by  evap- 
orating it  once  or  twice  to  dryness  with  excess  of  hydrochloric  acid. 

Interferences. — Should  this  test  fail  to  yield  a  metallic  deposit 
upon  the  copper,  it  would  not  follow  from  this  fact  alone  that 
arsenic  was  entirely  absent,  even  as  arsenious  acid,  since  the  deposi- 
tion of  the  metal  may  be  prevented  by  the  presence  of  certain  other 
substances.  Thus,  in  even  strong  solutions  of  the  poison  containing 
only  a  small  quantity  of  a  chlorate,  as  potassium  chlorate,  the  copper 
remains  perfectly  bright,  but  the  liquid  acquires  a  bluish  or  greenish- 
blue  color,  due  to  the  formation  of  a  soluble  salt  of  copper.  Should 
arsenic  and  a  chlorate  occur  in  the  same  mixture,  the  solution  is 
cautiously  evaporated  to  dryness,  and  the  dry  residue  fused  in  a  long, 
narrow  glass  tube  until  the  evolution  of  oxygen  ceases :  by  this 
operation  the  chlorate  will  be  converted  into  a  chloride,  and  the 
arsenic  into  arsenic  oxide.  The  tube  is  then  cut  into  small  pieces 
and  boiled  with  a  small  quantity  of  pure  water  until  the  saline  mat- 
ter has  entirely  dissolved,  and  the  solution  thus  obtained,  after  filtra- 
tion if  necessary,  is  saturated  with  sulphurous  acid  gas,  the  excess 
of  which  is  afterward  expelled  by  a  gentle  heat.  The  solution,  which 
now  contains  the  arsenic  as  arsenious  acid,  together  with  the  chloride 
resulting  from  the  decomposition  of  the  chlorate,  may  be  acidulated 
with  hydrochloric  acid  and  examined  in  the  usual  manner. 

So,  also,  the  presence  of  manganese  dinoxide,  and  of  other  sub- 
stances that  decompose  hydrochloric  acid  with  the  elimination  of 
free  chlorine,  may  interfere  with  the  reaction  of  the  test.  And  the 
same  is  true  of  free  nitric  acid.  This  acid,  however,  has  little  action 
upon  the  test  unless  present  in  quite  notable  quantity  or  the  solution 
be  concentrated  to  a  small  volume,  when  it  acts  upon  and  dissolves 
the  copper.  In  case  of  the  presence  of  free  nitric  acid,  the  solution 
may  be  neutralized  with  potassium  hydrate,  then  acidulated  with 
hydrochloric  acid,  and  tested  as  usual ;  or  the  solution  may  be  cau- 
tiously evaporated  to  dryness,  the  residue  dissolved  in  water,  this 
solution  saturated  with  sulphurous  acid  gas,  then  gently  heated  to 
expel  the  excess  of  gas,  and  examined. 

The  alkaline  nitrates  have  little  or  no  effect  upon  the  test  until 
the  solution  is  evaporated  to  near  dryness,  when  they  cause  the  solu- 


marsh's  tkst.  279 

tion  of"  the  copper.  In  a  mixture  coiitaiiiiiij;^  the  l-5tli  of"  its  weijrht 
of  potassium  nitrate  and  l-500tli  of"  arsenious  oxide,  the  reaction 
takes  place  much  the  same  as  in  a  pure  sohition  of  the  oxide. 

In  conclusion,  it  may  be  remarked  that  this  method  of  Keinsch 
possesses  several  advantages  which  entitle  it  to  more  consideration 
than  it  has  usually  received  at  the  hands  of  chemists.  Thus,  it  is 
easily  and  quickly  applied,  requiring  but  little  apparatus,  and  that 
of  the  most  simple  kind  ;  it  usually  requires  the  purity  of  only  one 
substance,  namely,  the  hydrochloric  acid,  to  be  known,  and  this  is 
readily  established  by  means  of  the  test  itself;  it  requires  no  dilution 
of  the  suspected  liquid,  but,  on  the  contrary,  permits  its  concentration 
to  almost  any  extent  while  the  test  is  being  applied  ;  it  may  be  applied 
directly  to  much  more  complex  organic  mixtures  than  either  of  the 
other  tests  for  this  poison ;  and,  finally,  it  serves  to  separate  from 
complex  mixtures  and  reproduce  in  an  unequivocal  form  a  less 
quantity  of  the  poison  than  any  other  known  test,  except,  perhaps, 
one  of  the  methods  of  Marsh's  process,  with  which,  however,  it  is 
about  equally  delicate. 

5.  Marshes  Test. 

"When  metallic  zinc  is  treated  with  diluted  sulphuric  acid,  the 
hydrogen  of  the  latter  is  displaced  by  the  metal  with  the  formation 
of  zinc  sulphate,  the  hydrogen  displaced  passing  off  in  its  free  state : 
Zn  +  H2SO^=ZnS04  +  H2,  If,  however,  arsenious  acid  or  arsenic 
acid  or  any  of  the  soluble  compounds  of  the  metal  be  present,  the 
nascent  hydrogen  decomposes  the  arsenical  compound,  and,  uniting 
with  the  metal,  forms  arsenuretted  hydrogen  gas,  ASH3,  which  is 
evolved  in  its  free  state.  The  reaction  in  the  case  of  arsenious  acid 
is  as  follows :  3Zn  +  SHgSO.H-  H3As03=3ZnSO,-f  3H2O+  AsHg ; 
with  arsenic  acid:  4Zn-}-4H2SO^+H3AsOi=4ZnSO,  +  4H20  + 
ASH3.  When  the  arsenic  is  present  as  a  chloride,  it  yields  hydro- 
chloric acid  and  the  arsenuretted  gas.  Xeither  metallic  arsenic  nor 
the  sulphides  of  the  metal  will  yield  a  trace  of  the  gas.  The  pro- 
duction of  arsenuretted  hydrogen,  under  these  conditions,  has  long 
been  known,  but  Mr.  Marsh,  of  Woolwich,  in  1836,  was  the  first  to 
employ  it  as  a  method  for  the  detection  of  arsenic. 

Arsenuretted  hydrogen  is  a  colorless,  extremely  poisonous  gas, 
having  a  peculiar  alliaceous  odor,  and  specific  gravity  of  2.695;  it  is 
neutral  in  its  reaction,  and  but  sparingly  soluble  in  water.     It  burns 


280 


AESENIC. 


with  a  bluish  flame,  giving  rise  to  arsenious  oxide,  and  is  readily- 
decomposed  by  heat  into  free  hydrogen  and  metallic  arsenic;  it  is 
also  readily  decomposed  by  solutions  of  the  easily  reducible  metallic 
oxides.  These  properties  serve,  in  the  manner  to  be  pointed  out 
hereafter,  for  the  detection  of  very  minute  traces  of  the  gas. 

Various  forms  of  apparatus  have  been  proposed  for  the  pro- 
duction of  this  gas  in  its  application  to  the  detection  of  arsenic,  but 
the  most  efficient  is  that  advised  by  Otto,  as  illustrated,  in  principle, 
by  Fig.  10.      The  gas-flask  A,  which  may  be  substituted  by  a  sim- 

FiG.  10. 


Apparatus  for  the  application  of  Marsh's  test. 


pie  wide-mouthed  bottle  or  in  delicate  experiments  by  a  long  test- 
tube,  is  provided  with  a  closely-fitting  cork  carrying  the  funnel-tube 
a  and  the  exit-tube  b  ;  this  tube  should  be  tolerably  wide,  and  have 
its  lower  end  cut  obliquely,  to  facilitate  the  dropping  back  of  any 
condensed  liquid  into  the  flask,  c  is  a  drying-tube  containing  frag- 
ments of  potassium  hydrate  or  of  calcium  chloride,  kept  in  their  place 
by  loose  cotton.  Unless  the  experiment  is  to  be  continued  for  some 
time,  it  is^only  necessary  to  fill  the  drying-tube  loosely  with  asbestos 


marsh's  test.  281 

moistened  with  coticentratt'd  sulplmric;  acid.  Tliis  tube  is  connected 
with  the  tube  h  by  means  of  a  perforated  cork,  and  with  the  reduc- 
tion-tube d  by  a  short  india-rubber  tube.  Tiie  reduction-tube  {d) 
should  be  of  hard  glass,  free  from  lead,  and  have  an  internal  diam- 
eter of  about  .'j-20ths  of  an  inch,  and  walls  not  less  than  the  l-20th 
of  an  inch  in  thickness;  its  outer  portion  should  ha  contracted  in  two 
or  three  places,  as  shown  in  the  figure,  and  terminate  in  a  turned-up, 
drawn-out  j)oint,  which  is  fused  in  a  small  flame  of  a  spirit-lamp 
until  tlic  opening  becomes  quite  small.  By  preparing  the  end  of  the 
tube  in  this  manner  there  is  no  danger  of  its  fusing  shut  when  the 
jet  of  gas  is  afterward  ignited.  In  very  delicate  experiments,  the 
bore  of  the  contracted  portions  of  the  tube  should  not  exceed  the 
l-20th  of  an  inch  in  diameter.  Several  of  these  tubes  should  be 
prepared  and  at  hand. 

About  two  ounces,  or  sixty  grammes,  of  pure  zinc,  either  granu- 
lated or  cut  into  very  small  pieces,  are  placed  in  the  flask  A,  and, 
the  apparatus  being  adjusted,  covered  with  a  cooled  mixture  con- 
sisting of  one  measure  of  pure  concentrated  sulphuric  acid  and 
four  measures  of  distilled  water,  added  through  the  funnel-tube  a, 
which  should  extend  to  near  the  bottom  of  the  flask.  The  zinc  will 
now  decompose  the  acid,  with  the  evolution  of  hydrogen,  in  the 
manner  before  described.  If  the  zinc  should  act  only  very  slowly 
upon  the  acid,  as  is  frequently  the  case  with  the  pure  metal,  the 
action  may  be  hastened  by  the  addition  of  a  few  drops  of  platinic 
chloride.  For  this  purpose,  it  is  sometimes  advised  to  add  a  little 
cupric  sulphate;  but,  according  to  M.  Gautier  [Ann,  d'Hyg.,  Jan. 
1876,  149),  the  addition  of  this  salt  is  attended  with  the  loss  of 
arsenic. 

Should  the  zinc  or  the  sulphuric  acid  be  contaminated  with  ar- 
senic, this  will  give  rise  to  arsenuretted  hydrogen.  Before,  therefore, 
applying  the  test  to  a  suspected  solution,  the  purity  of  the  materials 
employed  must  be  fully  established.  For  this  purpose,  after  the 
apparatus  has  become  completely  filled  with  hydrogen  and  while  the 
gas  is  still  being  evolved,  the  outer  uncontracted  portion  of  the  re- 
duction-tube is  heated  to  redness,  as  illustrated  in  the  figure,  for 
about  fifteen  minutes  or  longer.  If  this  fails  to  produce  a  metallic 
deposit  or  stain  in  the  contracted  part  of  the  tube,  in  advance  of 
the  part  heated,  the  material  may  be  considered  free  from  arsenic. 
The  purity  of  the  materials  having  been  thus  established,  it  may  be 


282  ARSENIC. 

necessary  to  wash  and  renew  the  zinc,  dry  the  tubes,  and  add  a  fresh 
portion  of  the  diluted  acid. 

Sulphuric  acid  in  its  concentrated  state  should  not  be  added  to 
the  zinc  mixture,  since,  as  first  shown  by  H.  Kolbe  [Ding.  Poly. 
Jour.,  April,  1872,  160),  and  confirmed  by  our  own  experiments,  if 
the  undiluted  acid  be  brought  in  contact  with  the  metal  in  the  pres- 
ence of  nascent  hydrogen,  it  may  be  reduced  with  the  formation  of 
sulphuretted  hydrogen,  which  might  in  part  or  wholly  retain  any 
arsenic  present  by  converting  it  into  arsenious  sulphide.  When  the 
acid  is  diluted  with  about  twice  its  volume  of  water  this  reduction 
does  not  take  place. 

The  apparatus  being  adjusted  and  completely  filled  with  evolved 
hydrogen,  the  jet  of  gas,  as  it  issues  from  the  drawn-out  end  of  the 
reduction-tube,  is  ignited,  care  being  taken  not  to  apply  a  light  until 
the  whole  of  the  atmospheric  air  is  expelled  from  the  apparatus,  as 
otherwise  an  explosion  might  occur.  A  small  quantity  of  the  arsen- 
ical solution  is  then  introduced  into  the  funnel-tube,  and  washed  into 
the  flask  by  the  subsequent  addition  of  a  few  drops  of  the  diluted 
sulphuric  acid.  The  decomposition  of  the  arsenical  compound,  with 
the  evolution  of  arsenuretted  hydrogen,  will  commence  immediately. 
The  presence  of  the  arsenuretted  gas  may  be  established  by  three 
different  methods, — namely  :  «■  By  the  properties  of  the  ignited  jet; 
/?.  By  decomposing  it  by  heat  applied  to  the  reduction-tube ;  and,  y. 
By  its  action  upon  a  solution  of  silver  nitrate. 

a.  The  ignited  jet. — As  soon  as  the  arsenical  solution  is  intro- 
duced into  the  flask  the  evolution  of  gas  increases ;  this  increase  is 
quite  perceptible  even  when  the  liquid  within  the  flask  contains  only 
the  1-1 ,000,000th  of  its  weight  of  arsenious  oxide.  The  flame  of  the 
ignited  jet  will  now  increase  in  size,  acquire  a  bluish  tint,  and,  unless 
only  a  minute  quantity  of  arsenic  is  present,  evolve  white  fumes  of 
arsenious  oxide;  so,  also,  sometimes,  the  flame  emits  a  peculiar  alli- 
aceous odor.  If  the  white  fumes  thus  evolved  be  received  upon  a 
cold  surface,  as  an  inverted  watch-glass,  they  condense  to  a  white 
powder,  which  sometimes  contains  octahedral  crystals.  The  arsenical 
nature  of  this  ])owder  may  be  shown  by  any  of  the  methods  hereto- 
fore pointed  out  for  the  recognition  of  solid  arsenious  oxide.  This, 
however,  is  by  no  means  a  delicate  method  for  detecting  the  presence 
of  the  arsenuretted  gas;  and  it  should  never  be  employed  to  the 
exclusion  of  that  now  to  be  mentioned. 


marsh's  tf,st,  283 

If  tlie  flame  be  allowed  to  strike  a<rainst  a  cold  body,  as  a  piece 
o(^  white  porcelain  held  in  a  horizontal  position,  it  yields  a  deposit 
of  metallic  arsenic  on  the  cold  surface.  In  exj)oriment.s  with  very 
dilute  solutions,  the  porcelain  should  be  applied  immediately  after 
the  introduction  of  the  arsenical  compound,  since  the  evolution  of 
the  arscnurettcd  gas  begins  at  once,  uiid  the  whole  of  the  metal  may 
be  thus  rapidly  evolved.  As  soon  as  a  well-marked  deposit  is  ob- 
tained on  the  porcelain,  the  position  of  the  latter  should  be  changed, 
so  that  the  tlame  may  strike  upon  a  fresh  surface :  if  it  can  be  done, 
a  number  of  these  deposits  should  be  collected  upon  several  different 
pieces  of  the  porcelain. 

When  the  amount  of  arsenic  present  is  not  very  minute,  the  cen- 
tral portion  of  the  deposits  thus  obtained  presents  a  bright  steel-like 
appearance;  this  is  surrounded  by  a  darker  and  less  lustrous  portion, 
the  outer  margin  of  which  has  sometimes  a  brownish  color.  The 
exact  appearance  of  these  deposits,  however,  depends  much  upon  the 
quantity  of  arsenic  present,  the  character  of  the  flame,  and  the  po- 
sition occupied  by  the  porcelain  :  sometimes  they  consist  simply  of 
brownish  stains,  whilst  at  other  times  they  are  in  the  form  of  rings. 
From  very  dilute  solutions  they  are  produced  only  when  the  gas 
burns  with  a  small,  steady,  round  flame  ;  when  the  supply  of  gas  is 
so  rapid  as  to  produce  a  long,  pointed  flame,  they  are  sometimes  not 
obtained  from  even  strong  solutions  of  the  metal.  When  the  gas 
burns  with  a  conical  flame,  the  porcelain  should  be  applied  at  about 
the  centre  of  its  upper  third  or  still  nearer  its  point;  on  the  other 
hand,  when  the  flame  is  short,  full,  and  round,  the  cold  surface 
should  be  held  very  near  its  base. 

Delicacy  of  this  method. — In  investigating  the  limit  of  this  tast 
in  regard  to  the  production  of  metallic  deposits  on  cold  porcelain,  a 
gas-flask  of  about  three  fluid-ounces  capacity  was  employed,  except 
when  the  entire  quantity  of  fluid  did  not  exceed  one  hundred  grain- 
measures,  when  the  flask  was  substituted  by  a  test-tube,  three-fourths 
of  an  inch  in  diameter  and  five  inches  long.  For  the  examination 
of  very  minute  quantities  of  arsenious  oxide,  or  of  any  other  soluble 
combination  of  the  metal,  a  test-tube  has  an  advantage  over  a  flask, 
in  that  the  arsenical  solution  can,  by  means  of  the  funnel-tube,  be 
brought  in  contact  with  the  zinc  and  be  thus  decomposed  before 
becoming  much  diffused  through  the  diluted  sulphuric  acid. 
1.  Yy^  grain  of  arsenious  oxide  in  solution  in  ten  grains  of  water, 


284  ARSEXIG. 

when  added  to  an  active  apparatus  containing  something  less 
than  an  ounce  of  pure  zinc  and  ninety  grain-measures  of  diluted 
sulphuric  acid,  yields  in  a  few  moruents,  from  the  ignited  jet, 
metallic  deposits,  which  continue  to  be  formed  until  about  sixty 
can  be  obtained,  after  which  the  evolved  gas  gives  no  evidence 
whatever  of  the  presence  of  the  metal.    The  degree  of  dilution  in 
this  case,  providing  the  poison  became  equally  diifused  through- 
out the  whole  of  the  liquid  in  the  apparatus,  would  be  one  part 
of  arsenious  oxide  in  100,000  parts  of  the  liquid  mixture. 
Of  six  experiments,  in  each  of  which  the  1-lOOOth  of  a  grain 
of  arsenious  oxide,  in  solution  in  ten  grains  of  water,  was  added  to 
an  active  apparatus  containing  two  hundred  and  ninety  grain-meas- 
ures  of  diluted   sulphuric  acid, — the  poison  now  forming  only  the 
l-300,000th  of  the  lic|uid  mixture, — the  highest  number  of  well- 
defined  deposits  obtained  was  sixty-seven,  the  lowest  fifty-two.    If, 
therefore,  none  of  the  metallic  arsenic  escaped  condensation, — which, 
however,  is  not  the  fact, — a  single  deposit  could  not  on  an  average 
have  represented  more  than  the  l-60,000th  of  a  grain  of  arsenious 
oxide,  or   only  about  the  l-80,000th  of  a  grain  of  the  metal ;  yet 
they  each,  with  very  few  exceptions,  measured  from  the  1-lOth  to 
the  l-14th  of  an  inch  in  diameter.     The  size  of  these  deposits  will 
of  course  depend  somewhat  upon  the  size  of  the  flame,  which  in  its 
turn  will  depend  upon  the  supply  of  gas  and  the  orifice  of  the  tube. 
Experiments  made  with  the  same  quantity  of  the  poison  in  the 
presence  of  five  hundred  grains  of  liquid — or   under  a  dilution  of 
500,000  parts  of  fluid — gave  much   the  same  results  as  those  just 
described. 

2.  YoTi)  grain  of  arsenious  oxide,   in   an   apparatus  containing  one 

hundred   grains   of  liquid,   or    under    a    dilution   of    250,000, 
furnished  as  the  average  of  six  experiments  twenty-nine  very 
satisfactory  deposits. 
The  same  quantity  of  the  poison  vafive  hundred  grains  of  liquid, 
or  under  a  dilution  of  1,250,000,  gave,  in  several  experiments,  sev- 
eral distinct  stains,  but  in  no  instance  were  the  results  satisfactory. 

3.  -g-yoT  g^'&i^  o^  arsenious  oxide,  in  one  hundred  grains  of  fluid,  or 

under  a  dilution  of  500,000,  usually  yields  several  satisfactory 
deposits.  But  the  same  quantit}^  of  the  oxide  in  three  hundred 
grains  of  liquid  failed  in  several  instances  to  yield  any  satis- 
factory evidence  of  its  presence. 


FALLACIES   OF   MARSH's  TEST.  286 

The  limit  of  tins  test,  as  applied  in  this  maiincr,  has  i)(!(;n  vari- 
ously assi!j;iu'(i  ;  but,  with  few  ex('e|)tions,  the  experinwMiters  have 
staled  only  the  degree  of  dilution  of  the  solution,  without  inention- 
iut;-  the  (piaiility  employed.  Thus,  it  has  been  stated  that  the  method 
will  yield  satisfactory  deposits  when  the  solution  contains  oidy  tlie 
l-2,000,000th  of  its  weight  of  arsenic.  This  is  true,  but  it  requires 
about  one  thousand  grains  of  such  a  solution  to  furnish  these  results; 
tiie  absolute  quantity  of  the  oxide  present  would  therefore  be  about 
the  l-2000th  of  a  grain.  These  statements  have  generally  led  to  a 
misapprehension  of  the  real  delicacy  of  this  test;  and  it  has,  there- 
fore, in  this  respect  been  much  overestimated.  It  is  a  fact  that  this 
method  of  Marsh,  when  referred  to  the  mixture  within  the  apparatus, 
will  indicate  the  presence  of  the  poison  under  a  greater  degree  of 
dilution  than  any  other  known  test ;  but  at  the  same  time  it  requires 
a  much  larger  quantity  of  the  solution  for  its  application  than  will 
serve  for  either  of  the  other  tests. 

From  the  experiments  already  cited,  it  would  appear  that  when 
one  hundred  grains  of  liquid  are  employed — and  this  is  about  the 
smallest  quantity  that  will  evolve  sufficient  gas  for  the  purpose — 
the  least  quantity  of  arsenious  oxide  that  will  yield  satisfactory 
deposits  is  about  the  l-5000th  of  a  grain.  This,  therefore,  so  far 
as  the  production  of  deposits  is  concerned,  is  about  the  limit  of 
the  test.  It  has  generally  been  conceded  that  this  method  would 
reveal  the  presence  of  a  smaller  quantity  of  arsenic  than  could  be 
recovered  by  the  method  of  Reinsch ;  but  this  is  not  the  fact,  since 
the  latter  process,  in  the  manner  already  described,  will  serve  to 
detect  a  much  less  quantity  of  the  poison  than  can  be  made  to  reveal 
any  evidence  of  its  presence  by  at  least  this  part  of  the  method  of 
Marsh. 

Fallacies. — Solutions  of  antimony,  under  these  same  conditions, 
undergo  decomposition  wath  the  production  of  antimonureited  hydro- 
gen, which,  like  arsenuretted  hydrogen,  burns  with  the  evolution  of 
white  fumes,  and  yields  metallic  deposits  upon  cold  surfaces  api)lied 
to  the  flame.  It,  however,  unlike  the  arsenuretted  gas,  is  destitute  of 
odor,  and  burns  with  a  greenish  flame;  moreover,  when  the  white 
fumes  evolved  are  condensed  on  a  cold  body,  they  yield  an  amorphous 
deposit,  which  is  insoluble  in  water,  and  immediately  assumes  an 
orange-red  color  when  moistened  with  a  solution  of  ammonium  sul- 
phide ;  whilst  that  obtained  from  arsenic,  under  similar  circumstances, 


286  ARSENIC. 

is  soluble  in  water,  and  undergoes  no  immediate  change  when  treated 
with  ammonium  sulphide. 

The  metallic  deposits  produced  by  antimonuretted  hydrogen  upon 
a  piece  of  cold  porcelain  are  usually  destitute  of  lustre,  and  have  a 
much  darker  color  than  those  obtained  from  arsenic.  These  charac- 
ters readily  serve  to  distinguish  between  comparatively  thick  crusts 
of  these  metals ;  but  in  very  thin  deposits  they  may  be  entirely  lost. 
The  deposits  of  the  two  metals,  however,  differ  greatly  in  regard  to 
their  chemical  properties.  1.  The  arsenical  crusts,  except  when  very 
thin,  are  only  very  slowly  soluble  in  a  drop  or  two  of  a  yellow 
solution  of  ammonium  sulphide;  whilst  tlie  antimonial  deposits  are 
readily  soluble  in  this  reagent.  When  the  ammoniacal  solution  is 
evaporated  to  dryness  on  a  water-bath,  the  arsenic  remains  as  a  bright 
yellotc  deposit  of  arsenious  sulphide,  which  is  readily  soluble  in  am- 
monia, but  insoluble  in  hydrochloric  acid;  under  the  same  condi- 
tions antimony  yields  an  orange-red  residue,  of  antimonious  sulphide, 
which  is  insoluble  in  ammonia,  but  readily  soluble  in  concentrated 
hydrochloric  acid.  This  method  will  serve  for  the  discrimination  of 
very  minute  deposits  of  the  metals.  2.  The  spots  produced  by  arsenic 
are  readily  soluble  in  a  solution  of  either  sodium  or  calcium  hypo- 
chlorite; whereas  those  from  antimony  are  insoluble,  or  dissolve  only 
after  prolonged  digestion,  in  a  solution  of  this  kind.  3.  The  deposits 
from  both  metals  readily  dissolve  in  a  drop  of  warm  nitric  acid,  and 
yield,  on  the  cautious  evaporation  of  the  liquid,  a  white  residue. 
When,  however,  the  arsenical  residue  is  touched  with  a  drop  of  a 
solution  of  silver  nitrate,  it  assumes  a  brick-red  color;  whilst  that 
from  antimony  remains  unchanged.  Various  other  methods  have 
been  proposed  for  distinguishing  between  these  stains,  but  in  point  of 
delicacy  they  are  much  inferior  to  those  already  described. 

Besides  this  fallacy  of  antimony,  it  has  been  objected  that  organic 
matter,  certain  combinations  of  iron,  phosphorus,  and  sulphur,  may 
under  the  above  conditions  yield  stains  somewhat  similar  to  those 
produced  by  arsenic.  But  neither  of  these  substances  will  yield  a  suc- 
cession of  spots ;  nor  will  either  of  them  yield  a  single  stain  having 
the  properties  described  under  either  of  the  three  methods  just  men- 
tioned for  the  identification  of  the  arsenical  deposit.  In  experi- 
ments for  the  purpose  with  mixtures  containing  iron,  phosphorus, 
and  sulphur,  we  have  failed  to  obtain  any  stain  whatever  having  the 
most  remote  resemblance  to  that  produced  by  arsenic;  nor,  in  numer- 


marsh's  tkst.  287 

ous  ai)|)lioati()ns  of  the  test  to  animal  and  vegetable   rnixliircs,  liave 
we  ever  found  it  to  yield  an  organic  stain. 

,?.  Decomposition  of  the  gas  by  heat. — As  originally  pro- 
posed by  Marsh,  this  test  consisted  simply  in  obtaining  metallic 
deposits  iVom  the  ignited  jet  of  gas,  as  now  desci-ibed.  Bcrzelius 
was  j>erlia|)s  the  first  to  resort  to  the  decomposition  of  the  arsenn- 
retted  gas  by  heat,  as  a  means  of  its  detection.  The  :ipi)ani(iis  being 
filled  with  hydrogen  and  the  evolution  of  gas  quite  moderate,  heat 
is  aj)plied  to  the  reduction-tube  at  a  point  about  one-half  or  three- 
quarters  of  an  inch  on  the  inside  of  the  outer  contraction.  When  the 
part  of  the  tube  to  which  the  flame  is  applied  is  quite  red  hot,  a 
very  small  quantity  of  the  arsenical  solution  is  introduced,  by  means 
of  the  funnel-tube,  into  the  flask.  The  arsenuretted  hydrogen  now' 
evolved,  as  it  passes  through  the  red-hot  ])ortion  of  the  reduction- 
tube,  will  be  decomposed,  with  the  production  of  a  deposit  of  metallic 
arsenic  in  the  contracted  part,  in  advance  of  the  flame.  After  a 
good  deposit  has  thus  formed,  the  heat  of  the  lamp  may  be  so  changed 
that  the  metal  may  be  deposited  in  the  second  contracted  portion  of 
the  tube. 

The  physical  appearance  of  the  deposits  thus  obtained  depends 
somewhat  upon  the  quantity  of  arsenic  present,  but  they  usually, 
especially  when  obtained  from  very  dilute  solutions,  consist  of  three 
conjoined  portions,  the  inner  of  which  is  transparent  and  of  a  brown 
color,  while  the  central  part  has  a  brilliant  metallic  appearance,  and 
this  fades  into  a  lighter-colored  or  gray  portion,  which  is  impercep- 
tibly lost.  Very  thick  deposits  may  present  much  the  same  charac- 
ters as  presented  by  the  sublimed  metal  already  described.  When  the 
quantity  of  arsenic  present  is  comparatively  large  and  the  current  of 
gas  rapid,  sometimes  arsenical  stains  may  be  obtained  from  the  ignited 
jet  at  the  same  time  that  a  deposit  is  being  formed  in  the  heated 
tube. 

Delicacy  of  this  method. — A  much  smaller  quantity  of  the  metal 
will  yield  deposits  by  this  process  than  will  serve  for  its  detection 
from  the  ignited  arsenuretted  gas.  This  difference  is  due  to  the  fact 
that  by  the  method  under  consideration  the  metal  eliminated  from 
the  decomposed  gas  may  be  collected  at  about  the  same  point  for 
several  minutes,  or  longer  if  necessary;  whereas  from  the  gas  when 
ignited  it  can  be  collected  at  the  same  place  for  only  a  few  moments. 
Another  advantage  of  this  method  over  the  preceding  is,  that  it  may 


288  ARSENIC. 

be  applied  with  a  less  quantity  of  liquid,  since  it  requires  only  a 

feeble  current  of  gas.     In  the  following  experiments,  one  hundred 

grain-measures  of  liquid,  including  the  arsenical  solution,  were  present 

in  the  apparatus,  and  the  reduction-tube  was  contracted  to  a  bore  of 

about  the  1— 20th  of  an  inch  in  diameter.     The  arsenious  oxide,  as 

introduced  in  the  apparatus,  was  in  solution  in  ten  grains  of  water. 

1.   2W0"  grain  of  arsenious  oxide,  in  one  hundred  grains  of  liquid, 

or  one  part  of  the  acid  in  the  presence  of  250,000  parts  of  fluid, 

yields  in  a  very  little  time  a  very  fine  deposit,  the  inner  portion 

of  which  has  a  brown  color,  while  the  outer  part  has  a  bright, 

metallic  lustre. 

grain,  under  a  dilution  of  500,000  parts  of  liquid,  yields 


1 


■"•     5000 

much  the  same  results  as  1. 

3.  x¥,Vro  grain,  under  a  dilution  of  1,000,000,  yields  a  quite  good 

deposit. 

4.  "2  s-.VoT  gi'3-in,  under  a  dilution  of  2,500,000,  yields  after  some 

minutes  a  very  satisfactory  deposit. 

5.  -g-o^o-  grain,  in  the  presence  of  5,000,000  parts  of  liquid,  yields 

after  several  minutes  a  very  distinct  stain,  the  outer  part  of 
which  has  a  dark,  metallic  appearance,  and  the  inner,  a  brown- 
ish color. 
In  regard  to  the  delicacy  of  this  method,  it  may  be  remarked 
that  in  the  whole  range  of  chemical  tests  there  is  perhaps  no  other 
that  will  indicate  the  presence  of  a  substance  under  as  great  a  degree 
of  dilution. 

Fallacies. — Antimonuretted  hydrogen  also  is  decomposed  under 
the  above  conditions,  with  the  deposition  of  metallic  antimony. 
Since,  however,  antimonuretted  hydrogen  is  decomposed  at  a  lower 
temperature  than  the  arsenuretted  gas,  the  antimony  eliminated  is 
always,  in  part  at  least  and  from  dilute  solutions  wholly,  deposited 
before  reaching  the  part  of  the  reduction-tube  to  which  the  flame  is 
applied ;  when  it  yields  deposits  on  both  sides  of  the  flame,  the  outer 
one  is  quite  near  the  flame.  On  the  other  hand,  arsenic  deposits 
about  one-half  or  three-quarters  of  an  inch  in  advance,  or  on  the  outer 
side  of  the  flame,  and  never  before  reaching  the  part  of  the  tube  to 
which  the  heat  is  directly  applied.  This  difference  in  itself  is  quite 
sufficient  to  distinguish  between  these  metals,  when  only  one  of  them 
is  present.  Again,  the  arsenical  deposit  has  usually  a  bright,  metal- 
lic lustre,  whilst  the  antimonial  has  a  dull  and  darker  appearance. 


marsh's  test.  289 

Very  thin  deposits  of  the  two  raetiils,  however,  may  present  very 
siiuihir  appearances. 

In  regard  to  the  action  of  heat  and  chemical  reagents  upon  these 
metallic  deposits,  they  differ  in  the  following  respects : 

a.  If  the  tube,  removed  from  the  apparatus,  be  heated  at  a  little 
distance  from  and  on  the  inner  side  of  the  crust,  and  the  heat  then 
slowly  advanced  to  it,  the  arsenical  deposit  readily  volatilizes  and 
recondenses  a  little  farther  on,  in  the  form  of  brilliant,  octahedral 
crystals  of  arsenious  oxide.  Under  the  same  circumstances,  the  anii- 
monkil  deposit  requires  a  much  higher  temperature  for  its  vaporiza- 
tion, and  re-deposits  quite  near  the  point  at  which  the  heat  is  applied, 
and  the  sublimate  produced  is  generally  amorphous,  or  consists  in 
part  of  minute  granules  and  opaque  granular  masses;  but  it  may 
contain  well-defined  octahedral  crystals  of  antimonious  oxide.  The 
arsenical  sublimate  may  be  further  identified  by  its  ready  solubility 
in  a  few  drops  of  hot  water,  and  by  the  resulting  solution,  when 
acidulated  with  hydrochloric  acid  and  treated  with  sulphuretted 
hydrogen  gas,  yielding  a  yellow  precipitate.  These  characters,  how- 
ever, reveal  themselves  only  in  sublimates  obtained  from  compara- 
tively tiiick  crusts  of  the  metal. 

b.  The  deposits  of  the  two  metals  may  also  be  distinguished  by 
either  a  solution  of  ammonium  sulphide,  or  of  sodium  hypochlorite, 
or  by  dissolving  the  crust  in  nitric  acid,  evaporating  the  solution  to 
dryness,  and  treating  the  residue  with  silver  nitrate,  in  the  manner 
already  described  for  the  discrimination  of  stains  obtained  on  por- 
celain from  the  ignited  gas. 

c.  If  a  slow  stream  of  perfectly  dry  sulphuretted  hydrogen  gas 
be  conducted  through  the  tube  containing  the  arsenical  deposit,  and 
the  latter  heated  by  a  flame  applied  to  the  tube,  beginning  at  the 
outer  margin  of  the  deposit,  it  in  vaporizing  is  converted  into  arse- 
nious sulphide,  which  condenses  at  a  little  distance  in  advance  of  the 
heat  to  a  yellow  deposit,  the  inner  margin  of  which,  even  after  cool- 
ing, has  sometimes  an  orange  hue.  The  metallic  deposit  from  the 
l-5000th  of  a  grain  of  arsenious  oxide  will  in  this  manner  yield 
very  distinct  results.  Under  these  same  conditions,  the  antimonial 
crust  also  decomposes  the  sulphuretted  gas,  with  the  formation  of 
antimonious  sulphide,  which,  however,  condenses  to  a  reddish-brown 
or  nearly  black  deposit.  To  effect  this  change  requires  a  stronger 
heat  than  for  the  arsenical  crust,  and  the  sulphide  formed  deposits 

19 


290  ARSENIC. 

much  nearer  the  flame  of  the  lamp.  In  applying  this  method,  it 
must  be  borne  in  mind  that  sulphuretted  hydrogen  alone,  especially 
if  moist,  may  be  decomposed  by  the  heat  with  the  deposition  of 
globules  of  sulphur,  which  while  warm  have  a  yellow  color,  but 
when  cold  they  have  only  a  very  faint  yellow  tint.  Arsenious  sul- 
phide is  readily  distinguished  from  free  sulphur  in  being  soluble  in 
ammonia.  When  exposed  to  a  slow  current  of  dry  hydrochloric  acid 
gas,  antimonious  sulphide  readily  disappears,  whilst  the  sulphide  of 
arsenic  is  unaffected  by  this  gas.  These  methods  of  distinguishing 
between  these  deposits  were  first  pointed  out  by  Pettenkofer  and 
Fresenius. 

There  is  no  other  metal,  besides  arsenic  and  antimony,  that  will, 
by  this  method  of  Marsh,  yield  a  deposit  in  the  heated  reduction- 
tube.  Sulphur  may  yield  a  yellowish -white,  and  selenium  a  reddish- 
brown,  stain ;  but  these  stains  could  not  be  confounded  with  the 
arsenical  deposit. 

y.  Decomposition  by  silver  nitrate. — If  the  reduction-tube 
of  the  apparatus  be  substituted  by  a  tube  bent  at  a  right  angle  (Fig. 
10,  e),  and  the  arsenuretted  hydrogen  conducted  into  a  solution  of 
silver  nitrate,  both  the  gas  and  the  silver  salt  undergo  decomposition, 
with  the  production  of  arsenious  acid,  which  remains  in  solution, 
and  the  elimination  of  metallic  silver,  which  falls  as  a  black  precipi- 
tate. The  reaction  in  this  case  is  AsH3+6AgN03+3H20  =  6Ag 
-f-HgAsOg+GHNOg.  The  resulting  solution,  therefore,  contains 
arsenious  acid  and  free  nitric  acid,  together  with  any  excess  of  silver 
nitrate  employed.  In  applying  this  test,  which  was  first  proposed 
by  Lassaigne,  the  current  of  gas  should  not  be  rapid,  and  only  a 
quite  dilute  solution  of  the  silver  salt  should  at  first  be  employed ; 
more  of  the  salt  may  afterward  be  added,  if  required. 

The  presence  of  the  arsenious  acid  thus  produced  may  be  shown 
by  either  of  the  following  methods : 

1.  If  the  solution  be  filtered,  and  the  filtrate  exactly  neutralized 
with  ammonia,  it  will  yield  a  yellow  precipitate  of  silver  arsenite, 
having  the  properties  already  described.  Should  the  whole  of  the 
silver  nitrate  have  been  decomposed  by  the  arsenuretted  hydrogen,  it 
will  of  course  be  necessary  to  add  a  little  of  this  salt,  after  the  neu- 
tralization by  ammonia,  before  the  precipitate  will  appear.  Since  in 
the  application  of  this  test  the  neutralization  of  the  eliminated  nitric 
acid  will  give  rise  to  ammonium  nitrate,  in  which  the  silver  arsenite 


FALLACIES   OF   MARSIl's   TEST.  291 

is  simringly  soluble,  the  ,-™c,i„„  will  not  be  c,uite  a.s  .lelleate  as  when 
the  (est  ,s  a|,,>l,e,l  lo  u  p„re  ,sol„li„„  of  arsenious  aeid. 

h  .  u,l,  an,l    he  h „,ue  t.eute.l  with  sulphuretted  hydrogen  g^  it 
yields  a  br,ght  yellow  preeipitate  of  arseoious  sulpbi.le      Tife  ar 
sen,e  fr„.„  the  l-l()„Oth  of  a  grab,  of  arsenious  oxide  eun  in  tbi. 
.nanoer  be  reeovered  without  any  appreciable  loss.     Instead  of  treat- 
ing the  solution  with  sulphuretted  hydrogen,  after  the  removal  of  the 

KZeil  t;:^  ""■""  "^  "^''■"'^'"-'"  -'•"'  ■■'  -^  ^  --■-'>  -y 

3.  If,  after  the  removal  of  the  excess  of  silver  nitrate  by  the 
cautious  addition   of  hydrochloric   acid,   the  filtrate  be  cautiously 
evaporated  to  dryness,  the  arsenic  will  remain  as  a  white  deposit  of 
ursenie  a«rf,  which,  when  moistened  with  a  solution  of  silver  nitrate 
assumes  a  brick-red  color.  "uiaie, 

micacy  of  thh  readion-ln  the  following  investigations  the 
isenions  oxide  was  dissolved  in  ten  grains  of  pur^  water,  the  soint  on 
placed  ma  small  test-tube  with  a  k..  fragments  of  ziLc,  and  then 
^fficieiU  diluted  sulphuric  acid  added  to  evolve  a  slow'stream  of 
gas.  The  gas  thus  evolved  was  conducted  into  five  grains  of  a  dilute 
solution  of  silver  nitrate. 

1.  -rio  grain  of  arsenious  oxide  yields  a  gas  that  produces  a  copious 
black  precipitate  in  the  silver-solution. 

2-  nr'rir  g''ai"  yields  a  good  precipitate. 

3-  -nr.k^  grain  ■  a  black  deposit  soon  appears  in  the  immerse<l  end 

of  the  delivery-tube,  and  in  a  little  time  black  flakes  appear  on 
the  surface  of  the  silver-solution. 

4-  TW.W  grain :  after  some  minutes  a  distinct  deposit  forms  in  the 

lower  end  of  the  delivery-tube. 

the  Is!  *';f7°V'"'  '•''''<=''<'»  depends  partly  upon  the  fact  that 
the  aiseunretted  hydrogen  evolved  from  one  part  of  arsenious  oxide 
eliminates  six  and  a  half  parts  of  metallic  silver 

J-afecie^-A  solution  of  silver  nitrate  is  also  decomposed  by 
a  timonuret ted  hydrogen,  with  the  production  of  a  black  pLpitate 
In  bis  reaction,  liowever,  as  already  pointed  out  (<z«fe,  2.30),  the 
whole  of  the  antimony,  even  to  the  last  trace,  is  throw^  down  as 

detect  "'"""•  J"'  "'"'"^  "'"'  ""^^^f"-'  -'™  ">  -P-ate  Z 
detect  arsenic  in  the  presence  of  antimony,  even,  according  to  Dr 


292  ARSENIC. 

Hofmann^  when  the  mixture  consists  of  one  part  of  the  former  and 
one  hundred  and  ninety-nine  parts  of  the  latter  metal,  and  only  a 
minute  quantity  of  the  mixture  is  examined. 

So,  also,  will  sulphuretted  hydrogen  and  the  hydride  of  phos- 
phorus produce  black  precipitates  in  a  solution  of  silver  nitrate.  It 
is  obvious,  therefore,  that  the  mere  production  of  a  black  precipitate, 
in  the  silver-solution,  is  not  in  itself  direct  evidence  of  the  presence 
of  arsenic. 

When  arsenuretted  hydrogen  is  passed  into  a  solution  of  corrosive 
sublimate  it  produces  a  yellow  or  brownish-yellow  precipitate,  which, 
according  to  H.  Rose,  consists  of  AsjSHggClg, — the  reaction  being, 
perhaps,  2AsH3-f  6HgCl2=  6HC1  +  As23Hg2Cl,.  Antimonuretted 
hydroo'en,  under  like  circumstances,  produces  a  white,  flocculent  pre- 
cipitate, which  almost  immediately  turns  gray,  then  dark  gray  or 
almost  black.  The  reaction  of  the  arsenuretted  gas  is  extremely 
delicate.  Thus,  the  gas  evolved  from  the  1— 50,000th  of  a  grain  of 
arsenious  oxide  in  ten  grains  of  fluid  will  produce  a  quite  distinct 
yellow  deposit  in  the  lower  end  of  the  delivery-tube. 

Since  arsenuretted  hydrogen  is  thus  decomposed  by  salts  of  silver 
and  of  mercury,  as  well  as  by  free  chlorine,  nitric  acid,  and  certain 
other  substances,  if  either  of  these  be  present  in  the  flask  in  which 
the  o-as  is  being  generated,  the  latter  may  be  entirely  decomposed 
before  leaving  the  apparatus.  It  is,  therefore,  obvious  that  if  in  the 
examination  of  a  suspected  mixture  by  the  method  of  Marsh  it 
should  yield  negative  results,  it  would  not  follow,  from  this  fact 
alone,  that  arsenic  was  entirely  absent,  even  in  a  soluble  form. 

M.  Z.  Roussin  has  recommended,  for  the  evolution  of  the  hydro- 
gen in  the  application  of  Marsh's  test,  to  substitute  for  the  zinc 
metallic  magnesium,  which  may  now  be  obtained  in  its  pure  state. 
If  this  metal  be  employed,  before  introducing  the  arsenical  or  sus- 
pected solution  into  the  apparatus  the  evolved  gas  should  be  ex- 
amined by  passing  it  through  the  red-hot  reduction-tube  for  about 
ten  minutes,  for  the  purpose  of  testing  its  purity.  This  preliminary 
examination  is  necessary,  since  magnesium  is  sometimes  contaminated 
with  silicium,  which  might  give  rise  to  silicuretted  hydrogen,  with 
the  deposition  of  a  dark  brown  deposit  in  the  heated  tube.  This 
deposit,  however,  differs  from  an  arsenical  crust  in  that  it  is  un- 


bloxam's  method.  293 

affoc'ted  by  nitric  acid  and  by  a  solution  of  :i  liypochlorite,  it  being 

insoluble  in  tlu'so  liquids.     {Cheni.  News,  July,  1866,  27,  42.) 

Bloxam's  Method. — When  arsenious  acid  is  present  in  a  mix- 
tun*  in  wliioli  watoi-  is  being  deoomj)osed  by  a  galvanic  current 
instead  of  by  zinc  and  sulphuric  acid,  the  arsenical  compound  is  also 
decomposed  by  the  nascent  hydrogen  with  the  formation  of  ansenu- 
rettcd  hydrogen  gas.  Prof.  Bloxam  has  proposed  this  reaction  as 
a  ready  means  of  detecting  arsenic,  and  as  free  from  some  of  the 
objections  that  may  be  urged  against  the  method  of  Marsh. 

The  form  of  apparatus  he  employs  consists  of  a  two-ounce 
narrow-mouthed  bottle,  the  bottom  of  which  has  been  cut  off  and 
replaced  by  a  piece  of  vegetable  parchment  tightly  stretched  over  it 
and  secured  by  a  thin  platinum  wire.  The  bottle  is  furnished  with 
a  cork,  carrying  a  funnel-tube,  and  a  small  tube  bent  at  a  right  angle 
and  connected  with  the  reduction-tube  by  a  caoutchouc  connection ; 
through  the  cork  also  passes  a  platinum  wire  bent  into  a  hook,  inside 
of  the  bottle,  for  suspending  the  negative  plate.  The  bottle  is 
placed  in  a  glass  vessel  of  such  size  as  to  leave  a  small  interval 
between  the  two,  and  this  arrangement  placed  in  a  large  vessel  of 
cold  water;  an  ounce  of  diluted  sulphuric  acid  -is  then  introduced 
into  the  apparatus,  so  as  to  fill  the  bottle  and  the  outer  space  to 
about  the  same  level,  the  positive  plate  being  immersed  in  the  acid 
contained  in  this  outer  space. 

The  apparatus  being  thus  adjusted,  the  terminal  platinum  plates, 
each  measuring  about  two  inches  by  tiiree-quarters  of  an  inch,  are 
connected  by  means  of  broad  strips  of  platinum-foil  with  a  Grove's 
battery  of  five  cells ;  the  one  within  the  bottle  being  connected  with 
the  zinc,  and  that  in  the  outer  vessel  with  the  platinum  extremity 
of  the  battery.  When  the  bottle  has  become  filled  with  hydrogen, 
the  reduction-tube — which  may  be  constricted  at  several  places — is 
heated  to  redness  for  about  fifteen  minutes,  to  test  the  purity  of  the 
sulphuric  acid  employed.  The  liquid  to  be  tested  is  then  introduced 
into  the  bottle  by  means  of  the  funnel-tube,  and  the  gas  evolved  ex- 
amined in  the  same  manner  as  in  Marsh's  method.  If  the  mixture 
froths,  from  the  presence  of  organic  matter,  a  little  alcohol  may  be 
added.  The  author  of  this  method  states  that  by  it  the  1-1 000th 
of  a  grain  of  arsenious  oxide  can  be  detected  in  an  organic  mixture 
with  the  greatest  ease  and  certainty. 


294  AESENIC. 

When  the  metal  exists  in  the  form  of  arsenic  acid,  no  arsenu- 
retted  hydrogen  is  evolved  by  this  process.  When  in  this  form, 
however,  the  arsenic  may  be  made  to  respond  to  the  test  by  treating 
the  solution,  previous  to  its  introduction  into  the  apparatus,  with 
sulphurous  acid  gas  or  a  few  drops  of  a  solution  of  sodium  disul- 
phite,  and  heating  on  a  water-bath  until  the  sulphurous  odor  has 
disappeared.  The  introduction  of  a  few  drops  of  a  solution  of  sul- 
phuretted hydrogen  gas  into  the  apparatus  also  serves  to  reduce  the 
arsenic  acid,  as  the  arsenic  combines  with  the  nascent  hydrogen  in 
preference  to  the  sulphur;  even  when  large  excess  of  sulphuretted 
hydrogen  is  employed,  it  does  not  interfere  with  the  evolution  of 
the  arsenuretted  gas.  But  under  these  circumstances  a  deposit  of 
sulphur  may  form  in  the  reduction-tube  outside  of  the  arsenical 
deposit,  and  the  latter  may  consist  partly  of  arsenious  sulphide ;  the 
sulphide  of  arsenic  may  be  distinguished  from  free  sulphur  by  its 
deep  yellow  color,  and  its  ready  solubility  in  a  warm  solution  of 
ammonium  carbonate,  in  which  the  sulphur  is  insoluble. 

The  addition  of  sulphuretted  hydrogen  to  the  arsenical  solu- 
tion, under  the  above  circumstances,  would  precipitate  as  a  sulphide 
any  antimony  or  mercury  if  present,  in  which  form  neither  of  these 
metals  interferes  with  the  detection  of  arsenic.  Thus,  Prof.  Bloxam 
states  that  the  1-1 000th  of  a  grain  of  arsenious  oxide,  converted  into 
arsenic  acid,  by  the  action  of  hydrochloric  acid  and  potassium  chlo- 
rate, when  mixed  with  one  grain  of  tartar  emetic  and  excess  of 
sulphuretted  hydrogen,  and  the  mixture  introduced  into  the  decom- 
posing cell,  furnished  in  the  reduction-tube  a  distinct  deposit  of 
arsenic  free  from  antimony.  Similar  experiments  made  with  mix- 
tures of  arsenious  acid  and  corrosive  sublimate  furnished  equally 
good  results.  Without  the  addition  of  the  sulphuretted  hydrogen, 
the  antimony  and  mercury  are  deposited  upon  the  negative  plate; 
when,  however,  a  comparatively  large  quantity  of  the  former  metal 
was  present,  it  yielded  a  metallic  mirror  in  the  reduction-tube. 
[Quart.  Jour.  Chem.  Society,  xiii.  12,  338.) 

Various  other  modifications  of  Marsh's  method  have  been  pro- 
posed. Thus,  Fleitmann  has  advised  to  generate  the  hydrogen  by 
acting  upon  zinc  with  a  warmed  solution  of  potassium  hydrate,  in- 
stead of  diluted  sulphuric  acid.  Any  arsenic  now  added,  if  in  solu- 
tion, would  be  evolved  as  arsenuretted  hydrogen,  while  if  antimony 


bettendorff's  test.  295 

were  present  it  would  hi;  retained  in  tlie  metallic  state  by  the  al- 
kaline solution.  Zinc,  however,  acts  only  very  slowly  upon  the 
alkaline  solution,  and  even  if  iron  filin<i;s  he  added,  as  has  been  ad- 
vised to  hasten  the  action,  wo  do  not  lind  the  nu'thod  advisai)le. 

Dr.  K.  W.  Davy  has  proj)osed  to  enijdoy  an  anial<j;ani  of  sodium 
for  generating-  the  hydrogen,  and  thus  do  away  with  the  use  of  an 
acid  and  employ  two  metals  whieh  are  not  liable  to  arsenical  con- 
tamination. The  amalgam  ])roposed  consists  of  one  part  by  weight 
of  sodium  to  eight  or  ten  parts  of  mercury,  and  is  prepared  by 
moderately  heating  the  mercury  in  a  test-tube  and  then  adding  the 
sodium,  small  portions  at  a  time.  The  metals  readily  unite  to  form 
an  alloy.  The  contents  of  the  tube,  while  still  hot  and  liquid,  are 
poured  out  on  a  clean  plate,  and  when  cold  broken  into  small  lumps, 
which  are  preserved  in  a  well-stoppered  bottle. 

To  emjiloy  the  amalgam,  the  suspected  solution  is  placed  in  a 
test-tube,  a  small  })ortion  of  the  amalgam  added,  and  the  mouth  of 
the  tube  quickly  covered  with  a  piece  of  filtering-paper  moistened 
with  a  solution  of  silver  nitrate.  Any  arsenic  present  will  now  give 
rise  to  arseuuretted  hydrogen  and  cause  the  moistened  paper  to  acquire 
a  dark  brown  or  dull  black  color,  due  to  the  reduction  of  the  silver 
salt  by  the  evolved  arsenical  gas.  [Chem.  News,  Feb.  1876,  58.) 
The  delicacy  of  the  reaction  of  arseuuretted  hydrogen  with  silver 
nitrate  solution  has  already  been  pointed  out.  The  mere  reduction 
or  blackening  of  the  silver  salt,  however,  should  not  be  accepted  as 
positive  proof  of  the  presence  of  arsenic. 

Otis  Johnson  has  proposed  to  evolve  the  hydrogen  by  the  action 
of  metallic  aluminium  upon  a  warmed  saturated  solution  of  potas- 
sium hydrate.     {Chem.  News,  Dec.  1878,  301.) 

6.  Bettendorff's  Test. 

When  a  solution  of  arsenious  oxide  or  of  arsenic  oxide  is  added 
to  a  strong  hydrochloric  acid  solution  of  stannous  chloride,  the  arsen- 
ical compound  is  reduced  with  the  separation  of  metallic  arsenic. 
To  apply  this  test,  a  small  quantity  of  the  tin  chloride  is  dissolved 
in  about  half  a  drachm  or  two  cubic  centimetres  of  strong  hydro- 
chloric acid  contained  in  a  test-tube,  a  drop  or  two  of  the  arsenical 
solution  added,  and,  if  necessary,  the  mixture  gently  warmed,  when 
it  will  assume  a  brownish  color,  and  after  a  time  yield  a  brownish 
or  grayish-brown  precipitate  consisting  chiefly  of  metallic  arsenic, 


296  ARSENIC. 

the  liquid  becoming  colorless.  The  delicacy  of  the  reaction  is  some- 
what increased  by  adding  to  the  mixture  about  half  its  volume  of 
concentrated  sulphuric  acid. 

Under  the  action  of  the  test,  1-lOOth  of  a  grain  of  arsenious 
oxide  will  yield  an  immediate  brown  coloration,  and  after  a  time  a 
very  decided  precipitate.  l-10,000th  of  a  grain,  when  forming  only 
l-500,000th  of  the  hydrochloric  acid  mixture,  will  yield  a  marked 
brown  coloration,  and  after  a  time  a  perceptible  brownish  deposit. 
This  is  about  the  limit  of  the  reaction. 

Other  Reactions  of  Arsenious  Acid. — Various  other  tests 
have  been  proposed  for  the  detection  of  arsenious  acid,  but  in  regard 
to  both  delicacy  of  reaction  and  freedom  from  fallacy  they  are 
much  inferior  to  those  already  described.  Among  these  tests  may 
be  mentioned  the  following. 

1.  Lime-water  produces  in  solutions  of  the  oxide  a  white  precipi- 
tate of  calcium  arsenite,  which  is  readily  soluble  in  hydrochloric 
and  most  other  acids.  One  grain  of  a  1-1 00th  solution  of  arsenious 
oxide  yields  a  copious,  flocculent  precipitate,  which  soon  becomes 
granular;  a  similar  quantity  of  a  1-1 000th  solution  yields  a  very 
good  granular  deposit;  and  the  same  quantity  of  a  l-5000th  solution, 
a  slight  cloudiness.  The  whole  of  the  arsenic  may  be  withdrawn 
from  the  hydrochloric  acid  solution  of  the  arsenite  by  Reinsch's  test. 
The  lime  reagent  also  produces  white  precipitates  in  solutions  of 
several  other  acids. 

2.  Potassium  iodide  slowly  throws  down  from  concentrated  solu- 
tions of  arsenious  acid  a  white,  granular  precipitate,  which  adheres 
tenaciously  to  the  sides  and  bottom  of  the  test-tube  in  which  the 
experiment  is  performed.  The  deposit,  when  treated  with  hydro- 
chloric acid,  assumes  a  bright  yellow  color.  Ten  grains  of  a  l-50th 
solution  of  the  oxide  fail  to  yield  with  the  reagent  a  precipitate  for 
several  minutes ;  after  about  an  hour  a  copious  deposit  has  formed. 
If,  after  the  addition  of  the  reagent,  the  mixture  be  treated  with 
large  excess  of  hydrochloric  acid,  it  yields  an  immediate  orange- 
yellow  or  yellow  precipitate,  which  is  insoluble  in  hydrochloric  acid, 
but  readily  soluble  in  excess  of  arsenious  acid.  In  this  manner 
the  1-lOOth  of  a  grain  of  the  oxide  in  one  grain  of  water  yields  a 
copious,  orange-yellow  deposit ;  and  the  1-lOOOth  of  a  grain,  a  quite 
good  yellow  precipitate.    If  the  arsenious  acid  be  added  to  a  solution 


SEPARATION    FROM  ORGANIC   MIXTURES.  297 

of  potassium  iodide  in  large  excess  of  hydrochloric  acid,  the  same 
yellow  precipitate  sei)arates. 

3.  When  a  sohitioii  of  arsenious  acid  is  treated  with  excess  of 
caustic  potash  and  a  drop  of  a  solution  of  copper  sulphate,  the  mix- 
ture on  being  boiled  throws  down  a  red  precipitate  of  copper  sub- 
oxide, due  to  the  reducing  action  of  the  arsenious  acid,  the  latter 
remaining  in  solution  as  arsenic  acid.  In  the  addition  of  the  copper 
solution,  care  should  be  taken  to  avoid  an  excess,  otherwise  the  mix- 
ture will  also  yield  a  black  precipitate  of  copper  mouoxide,  which 
may  mask  the  color  of  the  suboxide.  Solutions  of  grape-sugar  and 
of  certain  other  substances  have  a  reducing  action  similar  to  that  of 
arsenious  acid. 

Separation  from  Organic  Mixtures. 

Suspected  Solutions. — Since  arsenious  oxide,  under  certain  con- 
ditions, is  only  sparingly  soluble  in  water,  before  applying  any 
chemical  tests  to  a  suspected  mixture  containing  solid  organic  matter 
it  should  be  carefully  examined  for  solid  particles  of  the  poison.  If 
the  mixture  contain  much  mechanically  suspended  matter,  the  whole 
may  be  placed  in  a  large  porcelain  dish,  water  added  if  necessary, 
and  the  mass  thoroughly  mixed  ;  the  larger  organic  masses  are  then 
carefully  removed,  the  remaining  contents  gently  rotated  in  the  dish, 
the  supernatant  liquid  decanted,  and  the  residue  carefully  examined, 
by  means  of  a  lens  if  necessary,  for  the  solid  oxide.  Any  white 
masses  or  particles  thus  found  are  washed  in  pure  water  and  allowed 
to  dry.  A  very  small  portion  of  the  dried  mass  is  then  heated  in 
a  small  reduction-tube,  and  any  sublimate  obtained  examined  by  the 
microscope.  Other  portions  of  the  mass  may  be  examined  by  any  of 
the  other  tests  already  described  for  the  recognition  of  the  oxide  in 
its  solid  state.  So,  also,  a  portion  may  be  dissolved  in  water  and  the 
solution  tested. 

Whether  the  poison  is  thus  discovered  or  not,  the  organic  solids 
are  returned  to  the  liquid  and  the  whole  intimately  mixed,  the  liquid 
then  filtered,  and  the  solids  on  the  filter  washed  with  distilled  water, 
the  washings  being  added  to  the  first  filtrate.  Should  the  mixture 
presented  for  examination  be  thick  from  the  presence  of  organic 
matter,  after  the  addition  of  water  and  before  filtration,  it  may  be 
acidulated  with  hydrochloric  acid  and  gently  boiled  for  ten  or  fifteen 
minutes.     The  filtrate,  obtained  by  either  of  these  methods,  is  con- 


298  AESENIC. 

centrated  to  a  convenient  volume,  measured,  and  a  given  portion  set 
aside  for  a  quantitative  analysis  if  necessary.  Another  portion, 
acidulated  with  hydrochloric  acid,  is  boiled  with  a  very  small  slip  of 
bright  copper-foil,  the  latter  not  being  added  until  the  liquid  has 
reached  the  boiling  temperature.  If  the  copper  quickly  receive  a 
coating,  it  is  removed  from  the  liquid,  and  fresh  slips  of  the  metal 
added,  as  long  as  they  receive  a  deposit.  Should,  however,  the  cop- 
per first  added  not  receive  a  metallic  coating,  the  boiling  should  be 
continued  until  the  liquid  is  evaporated  to  near  dryness  before  it  is 
concluded  that  the  poison  is  entirely  absent.  Any  slips  of  copper 
that  have  thus  become  coated  are  washed  by  the  aid  of  a  gentle  heat, 
first  in  pure  water,  then  in  water  containing  a  trace  of  ammonia,  and 
again  in  pure  water,  then  drained,  placed  on  filtering-paper,  and  dried 
in  a  water-bath.  One  or  more  of  the  coated  slips  are  then  heated 
in  an  appropriate  reduction-tube,  when  the  deposit,  if  consisting  of 
arsenic,  will  yield  a  sublimate  of  octahedral  crystals  of  arsenious 
oxide,  readily  identified  by  means  of  the  microscope. 

If  the  method  now  considered  should  fail  to  reveal  the  presence 
of  arsenic,  there  would  be  little  doubt  of  the  entire  absence  of  the 
.poison,  unless,  possibly,  there  was  also  some  other  substance  present 
that  interfered  with  its  deposition  upon  the  copper ;  at  the  same  time, 
if  the  copper  remained  bright,  it  would  be  quite  certain  that  mercury 
and  antimony  also  were  absent. 

Should  it  be  desired  to  pursue  the  investigation,  another  portion 
of  the  above  filtrate  may  be  examined  after  the  method  of  Marsh. 
Or,  the  liquid,  acidulated  with  hydrochloric  acid,  may  be  saturated 
with  sulphuretted  hydrogen  gas,  and  allowed  to  stand  in  a  moder- 
ately warm  place  until  the  precipitate  has  completely  subsided ;  the 
precipitate  is  then  collected  on  a  filter,  washed,  and,  if  it  contains 
organic  matter,  purified  in  the  manner  hereafter  described. 

Vomited  matters. — These  are  carefully  collected,  and  examined 
for  any  solid  particles  of  the  poison.  The  mass  is  then  diluted  with 
water,  strongly  acidulated  with  hydrochloric  acid,  and  kept  at  about 
the  boiling  temperature  for  about  twenty  minutes ;  after  the  mix- 
ture has  cooled,  the  liquid  is  filtered,  the  fihrate  concentrated,  aud 
then  examined  in  the  manner  directed  above.  It  need  hardly  be 
remarked  that  a  failure  to  detect  the  poison  in  the  vomited  matters 
would  not  in  itself  be  conclusive  evidence  that  it  had  not  been 
taken. 


SEPARATION    FROM    ORGANIC   MIXTURES.  21l9 

Contents  of  the  Stomach. — Before  pnKX'cdinf^  to  the  preparation 
of  the  contents  of  the  stoniacli  for  the  application  of  chemical  tests, 
thev,  as  well  as  the  inside  of  the  organ,  should  be  minutely  examined 
for  aiiv  of  the  poison  in  it^  solid  state,  in  the  manner  described 
above.  Any  white  particles  or  powder  thus  found  are  washed, 
dried,  and  tested  in  the  usual  manner  for  the  solid  poison.  The 
physical  appearance  and  condition  of  the  stomach  should  also  be 
carefully  notetl. 

The  contents  are  now  placed  in  a  clean  porcelain  dish,  and  the 
inside  of  the  stomach  scraped  and  washed,  the  scrapings  and  wash- 
ings being  added  to  the  contents  of  the  dish ;  or  the  tissue  itself 
may  be  cut  into  small  pieces,  and  these  added  to  the  contents.  After 
the  addition  of  water  if  necessary,  the  mass  is  intimately  mixed  with 
about  one-eighth  of  its  volume  of  pure  hydrochloric  acid,  and  main- 
tained at  near  the  boiling  temperature  until  the  organic  solids  are 
entirelv  disintegrated.  The  mixture  is  then  allowed  to  cool,  trans- 
ferred to  a  clean  muslin  strainer,  and  the  matters  retained  by  the 
strainer  washed  with  water:  the  strainer,  with  its  contents,  may  be 
reserved  for  future  examination,  if  necessary.  The  strained  liquid 
thus  obtained,  if  in  large  quantity,  is  concentrated  at  a  moderate 
heat,  again  allowed  to  cool,  and  then  filtered. 

A  given  portion  of  the  filtrate  thus  obtained  is  examined  by  the 
method  of  Reinsch,  successive  slips  of  the  copper  being  added  as 
long  as  they  receive  a  deposit.  Any  pieces  of  the  metal  that  have 
thus  become  coated,  after  being  thoroughly  washed  and  dried,  are 
heated  in  a  suitable  reduction-tube,  and  the  result  examined  in  the 
usual  manner. 

Another  portion,  or  the  whole  of  the  remaining  filtrate,  may  be 
exposed  for  several  hours  to  a  slow  stream  of  Avaslied  sulphuretted 
hydrogen  gas,  then  gently  warmed,  and  allowed  to  stand  quietly 
until  the  supernatant  liquid  has  become  perfectly  clear.  If  the 
poison  is  present  in  considerable  quantity,  the  precipitate  may  have 
a  bright  yellow  color  and  consist  of  nearly  pure  arsenious  sulphide ; 
the  color  of  the  latter,  however,  may  be  much  modified  by  the  pres- 
ence of  organic  matter,  which  is  always  more  or  less  precipitated 
under  these  circumstances,  usually  of  a  yellowish-brown  color. 

The  precipitate  thus  produced  is  collected  upon  a  small  filter, 
washed,  and,  while  still  moist,  digested  with  pure  aqua  ammonise: 
this  liquid  will  readily  dissolve  any  arsenious  sulphide  present,  while 


300  AESENIC. 

the  organic  matter  may  remain  undissolved.  The  ammoniacal  solu- 
tion is  filtered,  and  the  filtrate  carefully  evaporated  at  a  moderate 
heat  to  dryness.  The  true  nature  of  the  residue  thus  obtained,  if 
consisting  of  arsenious  sulphide,  may  be  established  by  either  of  the 
methods  heretofore  pointed  out,  under  the  special  consideration  of 
the  sulphuretted  hydrogen  test.  Should,  however,  the  residue  con- 
tain organic  matter  and  only  a  minute  quantity  of  the  sulphide,  it 
may  require  further  purification  before  its  arsenical  nature  can  be 
satisfactorily  determined.  Under  these  circumstances,  the  dried 
residue  is  collected  in  a  thin  porcelain  dish  or  crucible,  moistened 
with  a  few  drops  of  concentrated  nitric  acid,  and  treated  in  the 
manner  described  hereafter,  for  the  purification  of  the  sulphuretted 
hydrogen  precipitate  obtained  from  the  tissues. 

The  contents  of  the  intestines  may  be  examined  in  the  same  man- 
ner as  the  contents  of  the  stomach.  Sometimes  the  poison  may  be 
detected  in  these  when  there  has  been  a  failure  to  show  its  presence 
in  the  stomach. 

From  the  Tissues. — Whether  the  examination  of  the  contents  of 
the  stomach  or  of  the  intestines  have  revealed  the  presence  of  arsenic 
or  not,  an  examination  of  the  tissues  or  fluids  of  the  body,  for  the 
absorbed  poison,  should  not  be  omitted.  Any  poison  found  under 
these  circumstances  would  be  that  which  had  entered  the  circulation 
and  had  its  share  in  producing  death ;  whereas  this  would  not  be 
the  case  with  that  found  in  the  contents  of  the  stomach  or  intestines. 
Moreover,  it  sometimes  happens  that  the  poison  is  absent  from  the 
alimentary  canal,  and  yet  readily  detected  in  some  of  the  tissues. 
Absorbed  arsenic  is  deposited,  to  a  greater  or  less  extent,  in  all  the 
soft  tissues  of  the  body,  and  any  of  these  may  be  made  the  subject 
of  analysis ;  the  greatest  relative  quantity,  however,  is  usually  found 
in  the  liver.  The  absolute  quantity  thus  found,  even  under  the 
most  favorable  circumstances,  rarely  exceeds  a  grain  in  weight. 

For  the  recovery  of  absorbed  arsenic  from  the  tissues  various 
methods  have  been  proposed.  In  many  instances  this  may  be  ef- 
fected by  simply  boiling  the  finely  divided  tissue  with  diluted  hy- 
drochloric acid  until  the  organic  matter  is  well  disintegrated,  and 
then  employing  the  method  of  Eeinsch.  In  this  manner  we  have, 
in  several  instances,  recovered  sufficient  of  the  poison  from  the  liver 
to  permit  its  confirmation  by  all  the  other  tests.  The  more  certain 
method  of  proceeding,  however,  is  to  destroy  entirely,  or  at  least 


SEPAUATIOX    FROM   TIIK   TISSUES.  301 

carbonize,  the  organic  matter  before  aj)i)Iying  any  tests.  For  this 
purpose  the  following  methods  have  been  advised. 

1.  Fresenius  and  Babo  proposed  to  destroy  or  disintegrate  the 
organic  matter  by  means  of  hydrochloric  acid  and  potassium  chlo- 
rate, under  the  action  of  heat.  For  this  purpose  we  have  found  the 
following  proportions  of  tissue,  acid,  and  the  chlorate  yield  very 
satisfactory  results.  Three  hundred  grammes,  or  ten  ounces,  of  the 
solid  tissue,  as  of  the  liver,  cut  into  very  small  pieces  and  placed 
in  a  clean  j)orcelain  dish,  are  treated  with  a  mixture  of  sixty  cubic 
centimetres,  or  two  fluid-ounces,  of  strong  hydrochloric  acid  and 
two  hundred  and  forty  cubic  centimetres,  or  eight  fluid-ounces,  of 
water.  The  mixture  is  heated  on  a  sand-bath,  and  when  at  about 
the  boiling  temperature,  about  one  gramme,  or  fifteen  grains,  of  pow- 
dered potassium  chlorate  added,  and  the  addition  repeated,  with 
frequent  stirring,  every  several  minutes,  until  about  six  or  seven 
grammes,  or  one  hundred  grains,  have  been  added  and  the  mass  has 
become  homogeneous  and  of  a  light  yellow  color.  During  this 
process  a  little  w^ater  should  occasionally  be  added,  to  prevent  con- 
centration of  the  liquid.  The  disintegrating  action  of  this  mixture 
is  chiefly  due  to  the  free  chlorine  and  chlorine  peroxide  evolved  by 
the  mutual  decomposition  of  the  chlorate  and  a  portion  of  the  hydro- 
chloric acid;  thus:  4KCIO3  +  12HC1  =  4KC1  +  GH^O  -f-  3Cia  + 
CJg.  The  disintegrated  mass  is  moderately  heated  until  the  odor  of 
chlorine  has  entirely  disappeared,  and  is  then  allowed  to  cool. 

The  cooled  mixture  is  transferred  to  a  linen  strainer,  and,  when 
the  liquid  has  all  passed,  the  solids  are  washed  with  a  little  w^arm 
water,  the  washings  being  collected  separately.  These  are  concen- 
trated on  a  water-bath  to  a  small  volume,  allowed  to  cool,  then  added 
to  the  first  strained  liquid,  and  the  mixed  liquid  filtered  through 
paper.     Any  arsenic  present  will  now  exist  as  arsenic  acid. 

The  filtrate  thus  obtained  is  exposed  to  a  slow  stream  of  sul- 
phurous anhydride,  known  also  as  sulphurous  acid  gas, — prepared  by 
boiling  slips  of  copper  with  concentrated  sulphuric  acid, — or  treated 
with  a  solution  of  acid  sulphite  of  sodium  (bisulphite)  until  it  smells 
strongly  of  the  gas.  Under  this  treatment  any  arsenic  acid  present 
will  be  reduced  to  arsenious  acid,  in  which  form  the  metal  is  not 
only  much  more  rapidly,  but  also,  as  we  have  found  by  experiment, 
more  completely  precipitated  by  sulphuretted  hydrogen  than  when 
it  exists  in  the  form  of  arsenic  acid.     The  reducing  action  of  the 


302  .  ARSExrc. 

gas  is  as  follows :  HgAsO^  -f  SO^  -^  H20  =  H2S04  +  HgAsOg.  The 
liquid  is  now  concentrated  on  a  water-bath  at  a  moderate  heat  to  a 
volume  twice  that  of  the  hydrochloric  acid  employed  in  preparing 
the  mixture.  We  have  found  that  the  liquid  may  be  concentrated 
quite  to  this  extent  witliout  any  loss  of  arsenic,  even  when  the  metal 
is  present  in  only  very  minute  quantity.  The  concentrated  liquid  is 
allowed  to  stand  in  a  cool  place  for  several  hours,  and  then  filtered. 

The  filtrate  thus  obtained  is  exposed  to  a  slow  stream  of  washed 
sulphuretted  hydrogen  gas  transmitted  through  the  liquid  for  several 
hours ;  it  is  then  gently  warmed,  and  allowed  to  stand  in  a  moder- 
ately warm  place  for  from  twelve  to  twenty-four  hours.  Any  arsenic 
present  will  thus  be  precipitated  as  arsenious  sulphide,  together  with 
more  or  less  organic  matter  and  free  sulphur.  Should  the  liquid 
contain  mercury,  antimony,  copper,  or  lead,  these  metals  would  also 
be  precipitated,  as  sulphides,  by  the  sulphuretted  hydrogen.  It  must 
be  borne  in  mind  that  liquids  prepared  as  the  above  usually  yield 
with  sulphuretted  liydrogen  a  brownish  or  yellowish  precipitate  of 
organic  matter  and  free  sulphur,  even  in  the  absence  of  any  metal. 
The  precipitate  is  now  collected  upon  a  small  filter,  and  washed,  at 
first  with  water  containing  a  little  sulphuretted  hydrogen,  until  the 
washings  no  longer  contain  chlorine. 

For  the  jjurification  of  the  precipitate  thus  obtained  different 
methods  have  been  proposed.  The  following  method,  advised  by 
Prof.  Otto,  has  in  our  hands  furnished  very  satisfactory  results. 
The  filter  containing  the  moist  precipitate  is  spread  out  in  a  porcelain 
dish,  and  the  precipitate  thoroughly  stirred  with  a  diluted  solution  of 
ammonia  ll  in  lOj,  which  will  readily  dissolve  any  arsenious  sul- 
phide present,  with  more  or  less  of  the  organic  matter  and  free 
sulphur:  one  part  .of  the  sulphide,  when  moist,  is  readily  taken  up 
by  forty  parts  of  the  diluted  ammonia.  The  sulphides  of  the  other 
poisonous  metals  mentioned  above,  which  might  be  present,  would 
remain  unchanged  under  the  action  of  the  ammoniacal  liquid,  except 
perhaps  a  mere  trace  of  the  antimony  sulphide.  The  ammoniacal 
mixture  is  transferred  to  a  small,  moistened  filter,  and  the  solid  resi- 
due washed  with  diluted  ammonia,  the  washings  being  collected  with 
the  first  filtrate.  The  filter,  with  its  contents,  should  be  reserved  for 
future  examination,  if  necessary. 

The  ammoniacal  filtrate,  which  has  usually  a  dark  brown  color, 
is  now  placed  in  a  small  porcelain  capsule  or  thin  evaporating-dish, 


SEPAItATIOX    FROM    THE   TISSUES.  303 

ami  eva|uir;\tiHl  to  dryness  on  a  watcr-hatli  ;  the  residue  is  treated 
with  a  small  qnanlity  of  eonceiitratcd  nitric  acid,  and  the  inixtnre 
ajjjain  evaporated  to  dryness,  this  operation  with  nitri(;  acid  l)ein<^ 
repeated,  if  necessary,  nnlil  the  moist  residue  has  a  vellow  color. 
The  residue  is  then  moistened  with  a  few  dro|)s  of  a  concentrated 
solution  of  caustic  soda,  a  small  quantity  of  pure  powdered  sodium 
carbonate  and  sodium  nitrate  added,  and  the  well-mixed  mass  cau- 
tiously evaporated  to  dryness;  the  heat  is  then  very  gradually  in- 
creased until  the  fused  mass  becomes  colorless,  when  the  ortranic 
matter  will  be  entirely  destroyed.  In  the  performance  of  the  oper- 
ations now  described  it  is  of  the  utmost  importance  that  the  nitric 
acid  and  the  sodium  compounds  employed  be  perfectly  free  from 
chlorine,  since  otherwise  a  portion  or  the  whole  of  the  arsenic  may 
be  volatilized  in  the  form  of  chloride. 

Any  arsenic  present  will  now  exist,  in  the  incinerated  residue,  as 
sodium  arsenate,  mixed  with  more  or  less  nitrate,  nitrite,  carbonate, 
and  sulphate  of  sodium,  the  latter  salt  being  derived  from  the  oxida- 
tion vof  the  sulphur.  This  mixture,  when  cooled,  is  dissolved  in 
a  small  quantity  of  warm  water,  and  the  solution,  after  filtration  if 
necessary,  strongly  acidulated  with  pure  sulphuric  acid,  then  evapo- 
rated until  fumes  of  sulphuric  acid  are  evolved.  By  this  treatment 
the  carbonic,  nitric,  and  nitrous  acids  will  be  entirely  expelled,  the 
sodium  combined  with  them  uniting  with  the  sulphuric  acid  to  form 
sodium  sulphate  :  the  solution  will,  therefore,  contain  only  sodium 
sulphate,  and  sodium  arsenate,  if  present.  Should  there  be  any  doubt 
as  to  the  entire  expulsion  of  the  nitric  and  nitrous  acids,  a  little  more 
sulphuric  acid  is  added,  and  the  solution  again  evaporated. 

Instead  of  destroying  the  organic  matter  by  fusion  with  sodium 
carbonate  and  nitrate  in  the  manner  above  described,  the  nitric  acid 
residue  mentioned  above,  after  addition  of  a  drop  of  caustic  alkali, 
may  be  treated  with  a  few  drops  of  concentrated  sulphuric  acid,  and 
the  mass  heated  on  a  sand-bath  until  it  becomes  about  drv ;  the 
residue  is  again  moistened  with  the  concentrated  acid,  and  heated  in 
the  same  manner  until  fumes  of  the  acid  are  no  longer  evolved. 
The  carbonaceous  residue,  pulverized  if  necessary,  is  then  boiled  with 
a  small  quantity  of  w^ater  containing  a  drop  or  two  of  sulphuric 
acid  ;  the  cooled  liquid  is  filtered,  and  the  carbonaceous  matter  washed 
with  warm  water  until  all  soluble  matter  is  removed.  If  in  the 
carbonization  the  whole  of  the  free  sulphuric  acid  was  expelled,  the 


304  ARSENIC. 

resulting  solution  will  be  colorless  and  entirely  free  from  organic 
matter.  The  liquid  may  now  be  concentrated  to  a  small  and  given 
volume.  This  method  is  somewhat  more  simple  and  expeditious 
than  that  described  above,  and  yields  about  equally  good  results. 

A  portion  of  the  final  solution  obtained  by  either  of  the  fore- 
going methods  may  now  be  introduced  into  an  active  Marsh's 
apparatus,  and  the  evolved  gas  examined  in  the  manner  already 
described.  Before  submitting  any  remaining  portion  of  the  suspected 
liquid  to  the  action  of  any  of  the  other  tests,  the  arsenic  acid  should 
be  reduced  to  arsenious  acid,  by  sulphurous  acid  gas,  in  the  manner 
heretofore  directed.  A  portion  of  the  solution  may  now  be  examined 
by  the  method  of  Eeinsch,  and  another  portion  submitted  to  the 
action  of  sulphuretted  hydrogen  gas.  Any  arsenious  sulphide  pre- 
cipitated from  a  solution  of  this  kind,  especially  if  only  a  small 
quantitv  of  the  metal  be  present,  will  usually  have  a  more  or  less 
brownish  or  orange  hue.  The  arsenical  nature  of  any  arsenious  sul- 
phide thus  obtained  may  be  confirmed  by  any  of  the  methods  here- 
tofore described,  especially  by  the  process  of  reduction.  If, the 
first  examination  of  the  suspected  liquid  by  Marsh's  method  indicate 
the  presence  of  a  comparatively  large  quantity  of  arsenic,  a  given 
portion  of  the  solution  should  be  employed  for  the  application  of 
the  sulphuretted  hydrogen  test,  and  the  quantity  of  the  sulphide 
thus  obtained  estimated  in  the  manner  hereafter  described.  If  any 
of  the  suspected  solution,  that  has  been  treated  with  sulphurous  acid 
gas,  still  remain,  and  it  be  desired  to  apply  the  silver  and  copper 
tests,  a  small  quantity  of  the  liquid  is  exactly  neutralized  by  caustic 
soda  or  sodium  carbonate,  then  divided  into  two  about  equal  parts, 
to  one  of  which  a  solution  of  silver  nitrate  and  to  the  other  a  solu- 
tion of  copper  sulphate  is  added,  when  any  arsenic  present  will  yield 
its  appropriate  precipitates.  Since,  under  the  circumstances  just 
mentioned,  the  arsenic  would  exist  in  the  neutralized  liquid  as  an 
alkali  arsenite,  the  ammonio-compounds  of  the  silver  and  copper 
salts  should  not  be  employed. 

The  method  now  described  for  the  disintegration  of  the  tissues, 
and  the  subsequent  purification  of  the  precipitate  produced  by  sul- 
phuretted hydrogen,  is,  according  to  our  experience,  the  best  yet  pro- 
posed for  the  recovery,  at  least  of  minute  traces,  of  absorbed  arsenic. 
At  the  same  time,  it  has  the  advantage  of  excluding  mercury,  anti- 
mony, and  certain  other  poisonous  metals  from  the  solution  tested 


SEPARATION    FROM   TlIK   TISSUES.  305 

for  arsenic,  and  yet  provides  for  tlieir  detection  if  present  in  tlie 
substance  submitted  to  examination.  In  illustration  of  the  delicacy 
of  this  process,  in  regard  to  the  purification  of  the  sulphuretted 
hvdr()<2;en  precipitate,  the  following  experiment  may  be  cited.  A 
partially  decomposed  liver,  free  from  arsenic,  was  boiled  with  diluted 
hydrochloric  acid  and  potassium  chlorate  until  the  organic  matter  was 
well  disintegrated,  and  to  one  thousand  fluid-grains  of  the  complex 
mixture  thus  obtained  the  1-lOOth  of  a  grain  of  arsenious  oxide, 
in  solution,  was  added, — the  oxide  forming  only  the  l-100,000th  of 
the  mixture.  The  mixture  was  then  gently  heated,  allowed  to  cool, 
and  the  strained  liquid  treated  with  a  slow  stream  of  sulphuretted 
hydrogen  for  twenty-four  hours;  the  precipitate  thus  obtained — 
which  purposely  contained  an  excess  of  organic  matter — was  then 
treated  as  described  above,  by  fusion  with  sodium  carbonate  and 
nitrate,  when  the  final  solution,  after  treatment  with  sulphurous 
acid  gas,  gave  with  several  reagents  results  that  could  scarcely  be 
distinguished  from  those  obtained  from  an  equal  volume  of  pure 
water  containing  the  1-lOOth  of  a  grain  of  the  poison. 

In  a  second  experiment,  the  1-lOOth  of  a  grain  of  arsenious 
oxide  was  added  to  the  tissue  of  a  stomach  and  its  contents  free  from 
arsenic,  the  added  arsenic  forming  only  l-600,000th  of  the  mixture, 
and  the  whole  treated  in  the  foregoing  manner  without  any  marked 
loss  of  the  arsenic. 

In  a  third  experiment,  the  1-lOOth  of  a  grain  of  arsenious  oxide, 
when  forming  only  the  l-600,000th  part  of  a  liver-mixture,  treated 
after  the  above  method  furnished  a  final  solution,  the  1-lOth  part  of 
which  in  each  case,  when  examined  respectively  by  Marsh's,  Keinsch's, 
and  the  sulphuretted  hydrogen  methods,  yielded  perfectly  satisfactory 
evidence  of  the  presence  of  arsenic. 

For  the  purification  of  the  sulphuretted  hydrogen  precipitate 
produced  from  organic  mixtures,  Fresenius  recommends  to  moisten 
it,  together  with  the  filter,  with  fuming  nitric  acid,  evaporate  to  dry- 
ness on  a  water-bath,  moisten  the  residue  with  warmed  concentrated 
sulphuric  acid,  then  heat  it  for  two  or  three  hours  on  a  water-bath, 
and  finally  on  an  oil-bath  to  a  temperature  of  about  170°  C.  (338° 
F.),  until  the  charred  mass  becomes  friable,  and  a  sample  of  it  no 
longer  imparts  a  color  when  mixed  with  water.  The  mass  is  then 
warmed  with  a  mixture  of  eight  parts  of  water  and  one  part  of 
hydrochloric  acid,  the  solution  filtered,  the  filtrate  precipitated  by 

20 


306  AESENIC. 

sulphuretted  hydrogen,  the  precipitate  collected  on  a  small  filter, 
washed,  redissolved  in  ammonia,  the  ammoniacal  solution  evaporated 
to  dryness,  and  the  residue  weighed.  The  residue  may  then  be  re- 
duced by  a  mixture  of  potassium  cyanide  and  sodium  carbonate,  in 
an  atmosphere  of  carbon  dioxide,  in  the  manner  already  described. 

In  this  connection  it  may  be  remarked  that  the  soft  animal  tis- 
sues may  be  broken  up  and  dissolved  by  heating  them,  after  being 
cut  into  small  pieces,  with  diluted  hydrochloric  acid  alone,  without 
the  subsequent  addition  of  potassium  chlorate.  But  under  these  cir- 
cumstances they  require  prolonged  heating,  and  the  resulting  solu- 
tion, when  strained,  is  apt  to  be  viscid  and  have  a  very  dark  or  nearly 
black  color,  both  of  which  are  objectionable  if  the  liquid  is  to  be 
subsequently  treated  with  sulphuretted  hydrogen.  A  more  serious 
objection,  however,  is  that  if  arsenic  be  present  in  the  form  of  sul- 
phide, which  is  not  unfrequently  the  case  when  the  parts  have  under- 
gone putrefaction,  the  whole  of  it  may  escape  solution.  To  a  liquid 
prepared  in  this  manner  the  method  of  Reinsch  may,  of  course,  be 
directly  applied ;  whereas  this  will  not  be  the  case  when  the  solution 
has  been  prepared  by  means  of  potassium  chlorate. 

That  the  method  of  Reinsch  will  serve  to  recover  very  minute 
quantities  of  arsenic  from  complex  solutions  is  well  illustrated  by 
the  following  experiment.  The  1-lOOOth  of  a  grain  of  arsenious 
oxide,  in  solution,  was  added  to  one  hundred  fluid-grains  of  the  com- 
plex mixture  obtained  by  boiling  a  stomach  with  its  contents,  free 
from  arsenic,  with  diluted  hydrochloric  acid.  The  mixture  was  then 
boiled  with  a  small  slip  of  bright  copper-foil,  when  after  a  little  time 
the  foil  received  a  very  good  steel-like  coating,  which,  when  heated  in 
a  small  contracted  reduction-tube,  furnished  a  fine  octahedral  crystal- 
line sublimate,  very  similar  to  that  obtained  in  a  like  manner  from 
the  1-lOOth  of  a  grain  of  the  oxide  in  solution  in  one  hundred  grains 
of  pure  acidulated  water.  It  will  be  observed  that  in  this  case  the 
poison  was  diffused  in  100,000  times  its  weight  of  the  organic  liquid. 

2.  For  the  recovery  of  absorbed  arsenic  from  the  tissues  M.  A. 
Gautier  has  recently  advised  the  following  method.  {Ann.  d'Hyg., 
Jan.  1876,  138.)  100  grammes  of  the  solid  tissue,  finely  divided 
and  placed  in  a  porcelain  dish  of  about  600  cubic  centimetres  capacity, 
are  treated  with  30  grammes  of  pure  nitric  acid,  and  moderately 
heated.  The  mass  slowly  liquefies  and  assumes  an  orange  hue.  The 
dish  is  then  removed  from  the  heat,  and  5  grammes  of  pure  sulphuric 


SEPARATION    FROM    THE   TISSUES.  307 

acid  added.  Tlic  mass  now  becomes  brown  and  is  violently  attacked. 
It  is  then  heated  till  vapors  of  sulphuric  acid  ap])ear.  The  residue 
is  treated  with  10  or  12  grammes  of  nitric  acid,  added  small  por- 
tions at  a  time;  this  causes  the  mass  to  again  liquefy,  and  it  evolves 
dense  nitrous  vapors.  When  all  the  acid  has  been  added,  the  mass 
is  heated  until  it  begins  to  carbonize.  The  easily  pulverized  residue 
thus  ol)tained  is  exhausted  by  boiling  water.  The  filtered  liquid,  of 
a  more  or  less  clear  wine  color,  is  treated  with  a  little  sodium  sulphite, 
and  the  arsenic  precipitated  as  sulphide  by  a  prolonged  current  of 
sulphuretted  hydrogen  gas.  The  sulphide  is  transformed  into  arsenic 
acid  in  the  ordinary  manner,  and  introduced  into  a  Marsh's  apparatus. 

In  experiments  after  this  method,  in  which  small  quantities  of 
arsenious  oxide  were  added  to  animal  tissues,  and  the  blood,  M. 
Gautier  recovered  very  nearly  the  total  theoretical  quantity  of  the 
metal.  And  in  our  own  experiments  the  method  has  given  very 
excellent  results.  On  applying  this  method,  however,  to  the  exami- 
nation of  300  grammes  of  the  liver  of  a  large  dog  killed  by  arsenic, 
0.32  milligramme  (l-200th  grain)  of  metallic  arsenic  was  obtained ; 
whereas  an  equal  quantity  of  the  same  organ  when  disintegrated  by 
hydrochloric  acid  and  potassium  chlorate,  and  the  solution  treated  as 
before,  furnished  0.52  milligramme  (1-1 25th  grain)  of  the  metal.  It 
may  be,  however,  that  in  this  instance  the  arsenic  was  not  equally 
distributed  throughout  the  liver. 

3.  Danger  and  Flandin  proposed  to  destroy  the  organic  matter  of 
the  tissues  by  means  of  concentrated  sulphuric  acid.  The  tissue,  cut 
into  small  pieces,  is  treated  with  about  one-fourth  its  weight  of  the 
concentrated  acid,  and  the  mixture  heated  in  a  porcelain  dish  until 
the  black  pasty  mass  first  produced  becomes  dry  and  carbonaceous ; 
the  cooled  mass  is  then  treated  with  a  little  concentrated  nitric  acid, 
or  aqua  regia,  and  again  evaporated  to  dryness.  The  mass  is  now 
treated  with  boiling  water,  the  solution  acidulated  with  nitric  acid, 
then  evaporated  to  dryness,  the  residue  moistened  with  nitric  acid, 
and  the  liquid  again  expelled  by  a  moderate  heat,  this  operation  with 
nitric  acid  being  repeated,  if  necessary,  until  the  mass  becomes  color- 
less. The  mass  is  then  dissolved  in  a  little  water,  the  solution  neu- 
tralized with  sodium  carbonate,  evaporated  to  dryness,  and  the  residue 
again  heated  with  a  few  drops  of  concentrated  sulphuric  acid.  Any 
arsenic  present  will  now  exist  as  sodium  arsenate.  The  residue  is 
then  dissolved  in  a  small  quantity  of  warm  water,  and  the  solution 


308  ARSENIC. 

examined  by  the  method  of  Marsh;  or,  the  solution  may  be  satu- 
rated with  sulphurous  acid  gas,  and,  after  gently  heating  the  liquid 
to  expel  the  excess  of  gas,  treated  with  sulphuretted  hydrogen. 

The  objection  to  the  method  of  Danger  and  Flandin  is  that  if  a 
chloride,  as  sodium  chloride,  or  common  salt  be  present,  the  carboni- 
zation with  sulphuric  acid  may  give  rise  to  the  volatilization,  in  the 
form  of  trichloride,  of  any  arsenic  present.  The  same  objection 
would  hold  against  the  employment  of  aqua  regia  in  the  process. 
To  meet  these  objections,  it  has  been  proposed  to  conduct  the  opera- 
tions in  a  retort  connected  with  a  well-cooled  receiver. 

4.  Duflos  and  Hirsch,  in  1842,  advised  to  treat  the  finely  divided 
tissue,  placed  in  a  retort,  with  about  an  equal  weight  of  pure  con- 
centrated hydrochloric  acid.  A  cooled  receiver,  containing  a  little 
water,  is  then  connected  with  the  retort,  and  the  latter  heated  on  a 
chloride  of  calcium  bath  until  the  contents  become  of  a  pasty  consist- 
ency. This  residue  is  mixed  with  about  twice  its  weight  of  strong 
alcohol,  the  mixture  allowed  to  digest  some  time,  the  liquid  then 
strained  through  muslin,  and  the  solid  matter  well  washed  with  fresh 
alcohol.  The  mixed  alcoholic  liquids  are  filtered,  and  the  filtrate 
distilled  in  a  retort  until  the  alcohol  passes  off,  after  which  the  residue 
is  mixed  with  the  acid  contents  of  the  receiver  of  the  first  distillation. 
This  mixture,  after  cooling,  is  treated  with  sulphuretted  hydrogen, 
when  any  arsenic  present  will  be  precipitated  as  sulphide. 

Since  arsenious  acid,  when  heated  with  concentrated  hydrochloric 
acid,  is  converted  into  arsenious  chloride,  which  is  volatile,  it  has 
recently  been  proposed  to  take  advantage  of  this  fact  for  the  complete 
separation  of  the  poison  from  the  tissues,  as  well  as  from  organic 
mixtures  generally.  The  finely  divided  tissue,  or  the  residue  obtained 
by  evaporating  the  suspected  organic  solution  to  dryness,  is  thoroughly 
dried  on  a  water-bath,  then  placed  in  a  retort  with  about  its  own 
weight  of  concentrated  hydrochloric  acid,  and  the  mixture  distilled 
on  a  sand-bath  to  almost  dryness,  the  distillate  being  collected  in  a 
well-cooled  receiver  containing  a  little  water;  the  residue  in  the 
retort  may  be  redistilled  with  a  fresh  portion  of  the  acid. 

The  distillate  thus  obtained  contains  the  arsenic  as  trichloride, 
together  with  a  large  quantity  of  free  hydrochloric  acid,  and  more 
or  less  organic  matter.  A  portion  of  the  distillate  may  be  examined 
after  the  method  of  Reinsch.  The  remaining  liquid,  diluted  if 
necessary,  is  examined  by  the  sulphuretted  hydrogen  test  or  by  the 


SEPARATION    PROM    THE    URINE.  309 

process  of  Marsh,  or  both,  and  the  results  confirmed  in  the  ordinary 
niannor.  Since  the  liquid  contains  a  large  quantity  of  free  hydro- 
chloric acid,  this  may  interfere  with  the  detection  of  minute  traces 
of  the  poison  by  the  method  of  Marsh.  The  only  metals,  besides 
arsenic,  that  could,  under  these  circumstances,  appear  in  the  distillate 
are  antimony,  bismuth,  and  perhaps  tin.  Should  the  arsenic  exist 
in  the  snl)stanco  subjected  to  distillation,  in  the  form  of  sul{)hide,  it 
would  not  appear  in  the  distillate.  Under  these  circumstances,  the 
residue  in  the  retort  may  be  heated  with  diluted  hydrochloric  acid 
and  the  occasional  addition  of  potassium  chlorate,  until  the  organic 
matter  is  destroyed ;  the  resulting  solution  is  then  treated  with  sul- 
phurous acid  gas,  and  subsequently  with  sulphuretted  hydrogen,  in 
the  manner  heretofore  described. 

So,  also,  if  the  arsenic  exists  as  arsenic  acid  it  will  not  appear 
in  the  distillate  as  trichloride,  unless  first  reduced  to  arsenious  acid. 
For  this  reduction  E.  Fischer  advises  (1880)  ferrous  chloride,  and 
he  finds  that  when  arsenic  acid  is  distilled  with  hydrochloric  acid  and 
ferrous  chloride,  it  is  quickly  reduced  and  completely  converted  into 
volatile  trichloride,  while  all  the  other  metals  of  the  sulphuretted 
hydrogen  group,  including  antimony  and  tin,  remain  behind  with 
the  iron. 

5.  As  an  easy  and  rapid  method  for  the  recovery  of  arsenic  from 
complex  mixtures,  T.  D.  Boeke  has  advised  {Chem.  News,  April, 
1880,  177)  to  heat  the  substance  with  hydrochloric  acid  and  potas- 
sium chlorate  until  the  mass  has  assumed  a  liquid  form.  The  liquid 
when  cold  is  filtered,  and  the  residue  washed  with  water.  The  yellow 
filtrate  is  treated  with  sodium  carbonate  to  strongly  alkaline  reac- 
tion, and  evaporated  until  sodium  chloride  begins  to  separate.  The 
liquid  is  then  again  treated  with  hydrochloric  acid  and  potassium 
chlorate,  filtered,  and  treated  with  excess  of  ammonia.  Addition  of 
-the  "magnesium  mixture"  will  now  precipitate  any  arsenic  present 
as  ammonium-magnesium  arsenate,  together  with  ammonium-mag- 
nesium phosphate.  After  twenty-four  hours  the  precipitate  is  col- 
lected, washed  with  diluted  ammonia  till  free  from  chlorine,  then 
dissolved  in  diluted  sulphuric  acid,  the  arsenic  acid  reduced  by  sul- 
phurous acid,  and  the  metal  precipitated  by  sulphuretted  hydrogen  as 
arsenious  sulphide. 

From  the  Urine. — A  large  quantity  of  the  urine,  as  250  c.c,  or 
8  fluid-ounces,  concentrated  to  a  syrup,  may  be  treated  with  sufficient 


310  ARSENIC. 

nitric  acid  to  decompose  the  urea^  and,  after  the  violent  action  has 
ceased,  the  liquid  evaporated  to  a  thick  syrup.  This  is  treated  with 
sulphuric  acid  and  heated  on  a  sand-bath  until  the  mass  is  nearly 
dry;  it  is  again  moistened  with  the  acid  and  heated  until  the  whole 
of  the  acid  is  expelled.  The  pulverized  residue  is  boiled  with  water 
containing  a  drop  or  two  of  sulphuric  acid,  the  liquid  filtered,  and 
the  solids  washed  with  water.  The  filtrate,  after  addition  of  sul- 
phurous anhydride,  is  concentrated  to  something  less  than  one-tenth 
the  volume  of  the  urine  employed,  or  until  saline  matter  begins  to 
separate.  It  is  then,  after  filtration  if  necessary,  treated  with  a  slow 
current  of  sulphuretted  hydrogen  gas,  and  any  arsenious  sulphide 
precipitated  purified  and  examined  in  the  manner  already  directed. 

The  urine  seems  to  be  the  principal  channel  through  which 
arsenic  is  eliminated  from  the  system.  In  a  case  related  by  Dr. 
Maclagan,  he  detected  a  trace  of  the  poison  in  twenty-six  ounces  of 
urine  as  late  as  the  twenty-first  day  after  it  had  been  taken.  In  a  case 
reported  by  Dr.  Gaillard  {Ann.  d'Hyg.,  Oct.  1874,  407),  a  young 
woman,  for  the  cure  of  an  obstinate  eczema,  took,  under  the  form 
of  Fowler's  solution,  one-fourth  grain  of  arsenious  oxide  daily  for 
fifteen  days ;  then  one-third  grain  for  the  same  period ;  and  finally 
one-half  grain  for  some  days.  Marked  symptoms  of  chronic  poison- 
ing having  appeared,  the  medicine  was  discontinued.  On  examina- 
tion of  the  urine,  arsenic  was  found  present,  and  it  continued  to  be 
eliminated  for  sice  and  a  half  weeks  after  the  medicine  had  been 
discontinued.  After  this  period  the  arsenical  paralysis  rapidly 
disappeared. 

Distribution  of  Absorbed  Arsenic. — It  was  first  announced  by 
Orfila,  in  1839,  that  when  arsenic  is  taken  into  the  system  it  is 
sooner  or  later  absorbed  and  distributed  to  the  blood,  tissues,  and 
various  secretions  of  the  body.  Subsequent  examinations  indicated 
that  the  absorbed  poison  was  for  the  most  part  usually  deposited  in 
the  liver,  kidneys,  and  spleen. 

More  recently,  however,  M.  Scolosuboif  concluded,  from  experi- 
ments upon  animals  poisoned  by  sodium  arsenite,  that  the  absorbed 
poison  was  deposited  chiefly  in  the  brain  and  spinal  cord ;  and  that 
if  the  absorbed  metal  present  in  a  given  quantity  of  fresh  muscle  be 
taken  as  1,  that  in  the  liver  is  10.8,  in  the  brain  36.5,  and  in  the 
spinal  marrow  37.3.   {Ann.  d'Hyg.,  1876, 153.)  More  recent  examina- 


DISTinHTTION    OF    ABSORHKU    ARSKNIC.  311 

tions,  however,  liave  shown  tliis  conchision  to  be  erroneous,  and  that 
usually  a  smaller  proportion  of  the  absorbed  poison  is  present  in  the 
nerve-tissue  than  in  eertain  other  tissues  of  the  body,  especially  the 
liver  and  kidneys. 

On  examining  the  liver,  brain,  one  kidney,  and  the  muscles  of  a 
man  who  died  from  the  effects  of  arsenic,  Prof.  Ludwig  foimd  the 
relative  ])roportions  of  arsenic  in  a  given  weight  of  the  different 
organs  to  be  as  follows  :  brain,  1  ;  muscles,  3  ;  liver,  84 ;  kidney,  129  ; 
that  is,  a  given  quantity  of  the  kidney  contained  129  times  more  of 
the  metal  than  was  found  in  an  equal  quantity  of  the  brain.  {Ann. 
(VHyg.,  Jan.  1882,  88.)  In  a  still  more  recent  case,  J.  Guareschi 
found  in  the  viscera  of  a  person  who  died  from  arsenical  poisoning, 
in  the  stomach  1.65  parts,  in  the  large  intestines  0.133,  in  the  liver 
0.105,  in  the  lungs  and  heart  0.6,  in  the  muscles  0.01  part,  and  in  the 
brain  only  traces  of  the  poison.  {Jour.  Chem.  Soc.  AbsL,  Feb.  1884, 
199.) 

In  an  experiment  in  which  a  large  dog  was  given  6.5  grammes 
of  arsenious  oxide  with  meat  during  a  period  of  eight  days,  and  was 
then  killed,  Profs.  Johnson  and  Chittenden  found  in  100  grammes 
of  the  different  organs  the  following  quantities  of  absorbed  arsenic : 
muscle,  0.2  milligramme;  kidneys,  0.4;  liver,  1.0  milligramme; 
whilst  from  the  entire  brain  only  a  faint  mirror  was  obtained.  (Amer. 
Chem.  Jour.,  Nov.  1880,  332.) 

In  a  judicial  case  examined  by  myself,  in  which  a  woman  had 
suffered  most  violent  symptoms  of  arsenical  poisoning  for  some  two 
or  three  days,  and  was  then  killed  by  blows  upon  the  head,  the 
largest  quantity  of  absorbed  arsenic  was  found  in  the  liver;  next  the 
kidneys;  less  in  the  spleen;  and  still  less  in  the  brain.  And  in  the 
instance  of  a  large  dog  killed  in  twenty-six  hours  by  twenty  grains 
of  arsenious  oxide  in  two  doses,  we  obtained  from  a  given  weight  of 
the  tissue  the  following  proportions  of  arsenic :  brain,  2  parts ;  kid- 
neys, 9;  liver,  17;  spleen,  18  parts. 

These  instances,  and  many  others  that  might  be  cited,  clearly 
show  that  there  is  no  exact  uniformity  in  the  distribution  of  the 
absorbed  poison,  but  that  as  a  general  result,  as  already  stated,  the 
largest  proportion  will  be  found  in  the  liver,  kidneys,  and  spleen. 
Doubtless,  as  remarked  by  Prof.  Johnson,  the  amount  that  may  be 
found  in  any  given  organ  or  tissue  Avill  depend  largely  upon  the 
readv  solubilitv  or  otherwise  of  the  form  under  which  it  was  taken. 


312  ARSENIC. 

and   the  length   of  time   the  individual  survived   after   taking  the 
poison. 

Failure  to  detect  the  Poison. — From  experiments  on  ani- 
mals Orfila  concluded  that,  if  there  is  no  suppression  of  the  natural 
secretions,  absorbed  arsenic  is  entirely  eliminated  from  the  living 
body  in  about  fifteen  days;  and  this  view  has  been  for  the  most 
part  sustained  by  observations  on  the  poisoned  human  subject.  In 
an  experiment  upon  a  dog,  Prof.  Ludwig  found  a  notable  quantity  of 
arsenic  in  the  Mwqv  forty  days  after  it  had  been  taken.  Independently 
of  the  action  of  absorption,  the  poison  may,  of  course,  be  rapidly 
removed  from  the  stomach  and  intestines  by  vomiting  and  purging. 
Thus,  Dr.  Taylor  relates  a  case  in  which  no  arsenic  was  found  in  the 
stomach  of  an  individual  who  died  in  eight  hours  after  taking  nearly 
two  ounces  of  the  poison.  [On  Poisons,  411.)  So,  also,  instances 
are  reported  in  which  death  took  place  within  a  few  days  after  the 
poison  had  been  taken,  and  none  was  found  in  any  part  of  the  body. 
According  to  the  observations  of  Dr.  Geoghegan,  the  liver  usually 
receives  its  greatest  quantity  of  absorbed  arsenic  in  about  fifteen 
hours  after  the  poison  has  been  taken,  when  the  organ  may  contain 
as  much  as  two  grains  of  arsenic.  A  case  is  reported  in  which  2.77 
grains  of  absorbed  arsenic  were  recovered  from  the  liver.  [Boston 
Med.  and  Surg.  Jour.,  Feb.  1880,  150.)  In  the  liver  of  a  dog  that 
had  been  under  the  influence  of  large  doses  of  the  poison  for  eight 
days  and  then  died  from  its  effects,  we  obtained  only  about  1-1 00th 
grain  of  arsenic.  It  must  be  remembered,  however,  that  the  poison 
may  be  entirely  absent  from  the  liver  and  yet  be  present  in  some  of 
the  other  organs  of  the  body.  In  a  case  related  by  Prof.  Casper 
[Forensic  Medidne),  in  which  death  occurred  in  twenty-four  hours, 
arsenic,  both  in  its  solid  state  and  in  solution,  was  readily  discovered 
in  the  contents  of  the  stomach,  but  neither  the  blood  nor  the  liver 
revealed  its  presence.  And  in  a  case  recorded  by  Grohe  and  Hosier, 
in  which  a  healthy  child,  two  years  old,  swallowed  a  green  arseni- 
cal paint  and  died  from  its  effects  in  seventeen  hours,  arsenic  was 
found  in  the  vomited  matters,  but  a  chemical  examination  failed 
to  reveal  its  presence  either  in  the  contents  of  the  stomach  and  intes- 
tines, or  in  the  spleen,  liver,  bile,  or  kidneys.  [Sydenham  Soc.  Rep., 
1867,  435.) 

Detection  after  long  periods. — If  arsenic  be  present  in  the  body 


POST-MO RTKM    DIFFUSION.  .".l.'i 

:it  the  time  of"  deatli,  tlic  iiu'tal  heiiii::  iiKlesinictible,  it  may  be  re- 
covered after  very  long  jjeriods.  A  ease  has  already  been  mentioned 
in  which  we  deteeted  the  poison,  both  in  its  absorbed  state  and  in 
the  stomaeh,  in  a  body  that  had  been  buried  seventeen  montlis ;  and 
another  in  which  it  was  found  after  the  lapse  of  three  and  a  half 
years.  In  a  ease  quoted  by  Dr.  Beck,  tiie  body  had  been  buried  for 
seven  years.  At  this  time  the  body  was  entire;  the  head,  trunk,  and 
shouklers  had  preserved  their  form  and  position,  but  the  internal 
orjrans  of  the  chest  and  abdomen  were  destroyed,  and  there  remained 
only  a  mass  of  soft,  brownish  matter,  which  was  deposited  along 
the  sides  of  the  spine.  A  chemical  examination  of  this  matter,  by 
MM.  Ozanam  and  Idt,  readily  revealed  the  presence  of  arsenic. 
{Med.  Ju)'.,  ii.  594.)  Prof.  Charles  H.  Porter  records  a  case  in 
which  he  found  about  three  grains  of  arsenic  in  a  body  that  had 
been  buried  eleven  years.  In  this  instance  the  liver  and  lungs  could 
still  be  recognized  by  their  structure.  {Medico -Legal  Contributions, 
Albany,  1862.)  i)r.  J.  W.  Webster,  of  Boston,  found  four  grains  of 
arsenic  in  the  body  of  a  woman  that  had  been  buried  in  a  vault  for 
fourteen  years.  This  seems  to  be  the  longest  period  yet  recorded  after 
which  the  poison  has  been  discovered  in  the  dead  body. 

Since  arsenic  exists  in  certain  soils,  it  is  sometimes  objected,  when 
the  poison  is  detected  in  an  exhumed  body,  that  it  may  have  been  de- 
rived from  the  surrounding  earth.  This  objection,  however,  has  no 
practical  force,  unless  only  a  very  minute  quantity  of  the  poison 
has  been  discovered  and  the  parts  of  the  body  examined  were  com- 
mingled with  the  earth.  Under  these  circumstances,  a  portion  of 
the  earth  may  be  separately  examined  for  the  poison.  The  quantity 
of  arsenic  present  in  arsenical  soils,  according  to  various  observers, 
never  exceeds  a  mere  trace,  and,  in  most  instances  at  least,  it  can  be 
extracted  only  by  the  stronger  mineral  acids. 

Post-mortem  Diffusion. — When  the  examination  for  absorbed 
arsenic  is  not  made  until  some  days  after  death,  it  may  be  a  question 
whether  any  metal  found  in  the  more  remote  organs  of  the  body 
was  really  carried  there  by  absorption  during  life,  or  whether  it 
found  its  way  into  the  organ  by  simple  post-mortem  imbibition  from 
some  other  organ  or  even  from  the  alimentary  canal. 

And  further,  as  first  announced  by  Orfila  long  since,  when  the 
examination  is  not  made  until  a  still  later  period,  it  may  be  impos- 
sible, from  chemical  analyses  alone,  to  determine  whether  any  poison 


314  AESENIC. 

found  had  been  taken  into  the  body  during  life  or  had  been  injected 
into  the  stomach  or  rectum  after  death. 

A  case  involving  this  question  was  tried  not  long  since  in  the 
State  of  Michigan.  {Jrjur.  Amer.  3Ied.  Assoc,  Aug.  1883 ;  also,  Arner. 
Jour.  Med.  Sei.,  Oct.  1883,  599.)  After  the  death  of  a  lady,  whose 
symptoms  strongly  pointed  to  arsenical  poisoning,  the  husband, 
with  a  view  of  preserving  the  body  for  removal,  claimed  to  have 
injected  arsenic  suspended  in  water  into  the  mouth  and  rectum.  One 
hundred  and  five  days  after  death  the  body  of  the  woman  was  disin- 
terred, and  the  stomach  and  rectum  placed  in  one  jar,  and  a  portion 
of  the  liver  and  one  kidney  in  another.  In  the  stomach  and  rectum 
together  Prof.  A.  B.  Prescott  found  about  twenty  grains  of  arseni- 
ous  oxide,  and  from  the  analysis  he  calculated  that  the  whole  liver 
contained  from  six  to  fifteen  grains,  according  to  the  size  of  that 
organ.  Later  the  body  was  again  disinterred,  and  the  bi^ain  and  a 
part  of  the  muscles  of  the  calf  of  the  leg  examined ;  but  in  these  no 
arsenic  was  found. 

The  chief  question  asked  the  six  experts  was,  '^pranting  that 
the  arsenic  was  injected  into  the  mouth  and  rectum  in  the  manner 
claimed,  could  it  reach  the  liver  and  other  organs  outside  the  ali- 
mentary canal?"    On  this  question  the  experts  were  equally  divided. 

As  bearing  on  this  question,  Drs.  Vaughan  and  Dawson  after- 
ward made  the  following  experiments  : 

About  fifty  grains  (3.24  grammes)  of  arsenious  oxide  suspended 
in  cold  water  were  injected  into  the  mouth  and  rectum  of  a  dead 
musk-rat,  and  the  animal  was  then  buried.  At  the  end  of  twenty- 
five  days,  the  lungs  were  found  to  contain  a  much  larger  amount  of 
the  arsenic  than  the  stomach,  the  larger  portion  of  that  injected 
having  evidently  passed  down  the  trachea.  Arsenic  was  found  in 
the  liver,  heart,  kidneys,  and  in  the  brain. 

In  the  second  experiment  a  cadaver  was  used,  the  body  having 
been  dead  between  two  and  three  days  when  the  injection  was  made. 
An  unweighed  quantity  of  arsenious  oxide  was  injected  into  the 
mouth  and  rectum,  and  the  body  placed  in  a  dry  cellar  for  twenty- 
five  days.  At  the  end  of  this  time  diffused  arsenic  was  found  in 
the  liver,  spleen,  heart,  and  again  in  the  brain. 

In  a  series  of  experiments  on  this  subject  by  Mr.  Frank  S.  Sutton, 
senior  student  in  medicine,  made  in  my  own  laboratory,  the  bodies 
of  dogs  killed  by  chloroform  were  employed.     In  each  case  three 


POST-MOKTKM    DIFFUSION.  315 

jjramrnes  of  arscnious  oxide  (liiruscd  in  50  c.c.  of  water  were  injected 
into  the  stomach,  and  an  equal  quantity  of  the  oxide  in  10  c.c. 
of  water  into  the  rcctnni.     Tlie  body  was  then  buried  in  the  earth. 

In  the  most  protracted  case  of  the  series,  in  which  the  injection 
was  made  twenty-three  liours  after  death,  and  the  body  was  disin- 
terred at  the  end  of  one  hundred  and  two  days,  ten  Miilligrammes 
(nearly  l-6th  grain)  of  arsenious  oxide  were  found  in  the  liver; 
and  the  metal  was  readily  detected  in  the  kidneys,  and  in  onr-fiffh 
of  the  final  solution  from  the  brain. 

In  three  other  cases  in  which  the  injections  were  made  in  from 
twenty-four  and  a  half  to  twenty-six  and  a  half  hours  after  death, 
and  the  bodies  examined  at  the  end  of  seventy-four,  forty-four,  and 
eighteen  days  respectively,  similar  results  were  obtained,  only  that  a 
gradually  diminishing  quantity  of  arsenic  was  found  in  these  organs. 

In  a  case  in  which  the  injection  was  made  six  hours  after  death, 
and  the  body  examined  at  the  end  of  ten  days,  arsenic  was  found  in 
the  liver  and  kidneys;  and  the  whole  of  the  final  solution  from  the 
brain  furnished  a  well-marked  mirror  by  Marsh's  method. 

When  the  injection  was  made  ten  minutes  after  death,  and  the 
body  examined  at  the  end  of  three  days,  the  final  solution  from  the 
brain  gave  a  well-marked  stain  in  the  reduction-tube  of  a  Marsh 
apparatus,  and  satisfactory  evidence  of  the  presence  of  the  metal  in 
the  liver  and  kidneys  was  obtained. 

But  when  the  injection  was  made  twenty-four  hours  after  death, 
and  the  body  examined  at  the  end  of  three  days,  the  final  solution 
from  the  brain  furnished  only  the  faintest  trace  of  arsenic.  The 
metal  was  present  in  very  minute  quantity  in  the  liver ;  but  it  seemed 
to  be  entirely  absent  from  the  kidneys. 

The  last  two  mentioned  experiments  show,  as  might  be  expected, 
that  if  the  injection  is  made  very  soon  after  death,  the  diffusion  takes 
place  more  readily  than  when  the  injection  is  not  made  until  some 
hours  after  death. 

It  has  sometimes  been  held  that  so  soon  as  decomposition  of  the 
body  with  evolution  of  sulphuretted  hydrogen  occurs,  post-mortem 
diffusion  will  be  arrested,  the  arsenic  being  converted  into  insoluble 
sulphide.  But  this  view  is  contradicted  by  the  results  of  the  fore- 
going experiments,  since  even  in  the  dogs  exhumed  at  the  end  of 
three  days  yellow  arsenious  sulphide  was  present.  According  to 
J.   Ossikovszky,  as  already   mentioned,  arsenious  sulphide   in   the 


316  ARSENIC. 

presence  of  decomposing  organic  matter  is  itself  after  a  time  decom- 
posed, the  metal  being  oxidized  to  arsenious  oxide  and  even  arsenic 
oxide.     The  latter  oxide  is  very  diffusible,  being  extremely  soluble. 

Arsenic  in  Chemicals,  Medicines,  and  Fabrics. — 1.  Since  sulphuric 
acid  and  metallic  zinc  are  very  liable  to  be  contaminated  with  arsenic, 
these  substances  should  be  carefully  examined  for  this  metal  before 
being  employed  in  judicial  analysis.  Both  these  substances  are  now 
more  readily  than  formerly  obtained  free  from  arsenic.  In  every 
instance  the  analyst  should  determine  the  purity  of  the  acid  and  the 
zinc  for  himself. 

2.  Arsenic  may  also  be  present  in  hydrochloric  acid  as  an  impurity, 
especially  in  what  is  known  as  the  commercial  acid.  To  test  the  acid, 
about  50  C.C.,  or  two  fluid-ounces,  are  treated  with  a  saturated  solu- 
tion of  stannous  chloride  and  about  half  a  volume  of  pure  sulphuric 
acid,  added  small  portions  at  a  time,  when  if  arsenic  is  present  the 
mixture  will  soon  present  a  brownish  turbidity,  and  after  a  time 
yield  a  brown  precipitate  of  the  metal.  In  a  sample  of  solution  of 
ferric  chloride  F.  W.  Fletcher  found  about  .06  per  cent,  of  arsenic ; 
and  in  others  about  .02  per  cent.,  due  to  an  impurity  in  the  hydro- 
chloric acid  employed  in  the  preparation  of  the  mixture.  {New 
Remedies,  Dec.  1880,  371.)  In  this  instance,  however,  the  impurity 
may  have  been,  in  part  at  least,  due  to  an  impurity  of  the  iron,  since 
J.  Mitteregger  found  in  a  sample  of  iron  as  much  as  1.7  per  cent,  of 
arsenic.     {Amer.  Chemist,  June,  1873,  471.) 

For  the  purification  of  arsenical  hydrochloric  acid,  A.  Betten- 
dorff  advises  to  treat  the  acid  with  stannous  chloride,  allow  the  mix- 
ture to  stand  twenty-four  hours,  then  separate  the  precipitate  and 
distil  the  acid,  collecting  the  first  1-lOth  separately,  the  remaining 
portion  when  distilled  being  entirely  free  from  arsenic.  [Chem.  News, 
Oct.  1869,  189.) 

3.  According  to  Dr.  Fresenius,  crystallized  commercial  sodium 
carbonate  sometimes  contains  a  perceptible  quantity  of  arsenic,  (kie 
undoubtedly  to  the  use  of  arsenical  sulphuric  acid  in  the  manufacture 
of  the  salt.     {Chem.  News,  Nov.  1869,  226.) 

4.  It  has  long  been  known  that  basic  bismuth  nitrate,  or  subnitrate 
of  bismuth,  is  rarely  free,  at  least  as  formerly  prepared,  from  at  least 
traces  of  arsenic,  and  sometimes  this  impurity  is  present  in  very 
notable  quantity.     Of  six  samples  of  the  nitrate  examined  by  Dr. 


IN   CHEMICALS,   MEDICINES,   AND   FABRICS.  317 

Gunning,  every  sample  contained  arsenic.  {Chem.  News,  May,  1868, 
260.)  According  to  Prof.  A.  Still6  {Tlicrap.,  i.  166),  .16  per  cent,  is 
the  laro;e.st  proportion  of  the  metal  that  has  been  found  in  any  sjjeci- 
nien  of  the  suhnitrate  presumed  to  be  pure.  Of  fourteen  samples  of 
the  salt  examined  by  Prof.  R.  H.  Chittenden  {Amer.  Chem.  Jour., 
Feb.  1882,  396),  only  one  was  found  entirely  free  from  arsenic;  the 
other  samples  contained  from  0.00435  to  0.07719  per  cent,  of  arsenic, 
calculated  as  arsenious  oxide,  the  average  of  the  samples  examined 
being  0.01302  per  cent.  Two  cases  of  non-fatal  poisoning  by 
arsenical  nitrate  of  bismuth  are  recorded  in  the  American  Journal 
of  the  Medical  Sciences  for  Jan.  1874,  280. 

In  order  to  determine  the  extent  of  the  absorption  of  arsenic 
from  bismuth,  when  present  as  an  impurity,  Prof.  Chittenden  gave 
a  dog  during  a  period  of  five  weeks  539  grammes  (8318  grains)  of 
the  salt  containing  66  milligrammes  (slightly  over  one  grain)  of 
arsenic,  the  amount  of  arsenic  given  with  the  bismuth  during  the 
last  three  weeks  being  2.38  milligrammes  (l-27th  grain)  per  day ;  the 
dog  was  then  killed.     Minute  quantities  of  arsenic  were  found  in 
the  stomach  and  intestines,  but  only  the  merest  traces  in  the  liver, 
blood,  kidneys,  and  muscles.     Of  the  bismuth,  only  minute  traces 
were  found  in  the  liver  and  the  blood.    From  the  experiments  of  the 
same  observer,  it  would  appear  that  arsenic  when  present  in  the  bis- 
muth salt  is  not  (at  least  generally)  in  the  form  of  arsenious  oxide  or 
any  soluble  form,  since  not  a  trace  of  arsenic,  in  a  sample  containing 
0.0117  per  cent,  was  extracted  by  large  quantities  of  boiling  water. 
The  arsenical  impurity  of  bismuth  nitrate  was  strongly  urged  by 
the  defence  in  the  case  of  State  of  Virginia  vs.  Emily  E.  Lloyd, 
charged  with  the  murder  of  her  child,  aged  about  four  years,  with 
arsenic.    (Leesburg,  Ya.,  1872.)    Bismuth  nitrate  with  a  little  opium 
had  been  prescribed  for  the  child  on  the  second  day  of  its  illness, 
death  taking  place  in  about  forty-eight  hours  after  the  symptoms 
first  appeared,  under  excessive  vomiting  and  purging,  and  great  pros- 
tration.    It  did  not  clearly  appear  in  evidence  that  the  bismuth  pre- 
scribed had  really  been  administered.    In  the  stomach  of  the  deceased 
Prof.  Tonry,  of  Baltimore,  readily  found  arsenic ;  but  as  the  coroner 
who  had  had  charge  of  the  jar  containing  the  stomach  died  before 
the  trial,  the  court,  very  properly,  excluded  the  results  of  the  analysis 
of  this  organ.     At  a  second  exhumation  of  the  body  made  before 
the  trial.  Dr.  Tonry  took  charge  of  the  liver,  spleen,  and  kidneys. 


318  ARSENIC. 

and  found  in  these  organs  the  equivalent  of  86-lOOths  grain  of 
arsenious  oxide.  Independent  examinations,  by  Prof.  J.  W.  Mallet 
and  myself,  of  samples  of  the  bismuth  salt  prescribed  for  the  child, 
showed  the  presence  of  minute  quantities  of  arsenic,  my  own  results 
indicating  0.012  per  cent.,  calculated  as  arsenious  oxide.  During 
the  trial  it  was  clearly  shown  that  the  prisoner  had  purchased  a 
quantity  of  arsenic  shortly  prior  to  the  death  of  the  child.  More- 
over, the  commonwealth  claimed  to  have  evidence  tending  to  prove 
that  previously  three  other  children  of  the  accused  had  died  under 
very  similar  circumstances ;  this  evidence,  however,  was  not  admitted. 
The  woman  was  acquitted. 

5.  Arsenic  is  also  not  unfrequently  present  in  minute  quantity  in 
tartar  emetic,  as  an  impurity.  It  is  said  that  this  salt  when  in  well- 
formed  crystals  is  always  entirely  free  from  arsenic.  To  examine 
tartar  emetic  for  this  impurity,  Strohmeyer  recommends  to  dissolve 
two  grammes  of  the  finely  pulverized  salt  in  four  grammes  of  pure 
hydrochloric  acid,  of  sp.  gr.  1.124,  then  add  to  the  solution  thirty 
grammes  more  of  the  acid  thoroughly  saturated  with  sulphuretted 
hydrogen,  and  allow  the  mixture  to  stand.  If  arsenic  is  absent,  the 
liquid  remains  perfectly  colorless ;  but  the  presence  of  the  slightest 
trace  of  the  metal  gives  rise  to  a  yellow  coloration,  and  after  a  time 
a  yellow  precipitate  of  arsenious  sulphide  is  formed.  [Chem.  News, 
Dec.  1869,  275.) 

6.  Arsenic  is  largely  used  in  the  arts  in  the  preparation  of  certain 
pigments.  Thus,  arsenite  of  copper,  or  Scheele^s  green,  and  the  aceto- 
arsenite  of  copper,  known  as  Schweinfurt  green,  are  largely  employed 
for  coloring  wall-papers  and  artificial  flowers;  and  arsenic  acid  is 
largely  used  in  the  manufacture  of  aniline  colors,  which,  especially 
the  various  shades  of  red,  often  retain  notable  quantities  of  the  metal. 
In  nine  wall-papers,  of  green  and  drab  colors,  examined  by  Mr.  A. 
S.  Parker  {Jour.  Amer.  Chem.  Soc,  July,  1880,  339),  the  proportion 
of  arsenic,  expressed  as  arsenic  oxide,  was  found  to  vary  from  0.216 
grammes  (3.3  grains)  to  4.840  grammes  (75  grains)  per  square  yard. 
Two  samples  of  green  cambric  contained,  respectively  per  square 
yard,  4.000  and  3.879  grammes  of  arsenic. 

For  the  separation  of  arsenic  from  fabrics  of  this  kind,  Mr. 
Parker  advises  to  dissolve  the  arsenic  from  the  material  by  hydro- 
chloric acid,  and  treat  the  filtered  solution  with  sufficient  potassium 
hydrate  to  precipitate  the  copper.     The  filtered  liquid  is  then  acidu- 


IN   GLASS.  310 

lated  and  treated  with  siilplui retted  liydrogen,  the  precipitate  oxidized 
with  nitric  acid,  and  heated  on  a  sand-hath  to  expol  the*  snlphuric 
acid  and  organic  matter,  the  residne  heing  weighc'd  as  arsenic  oxide. 
When  the  arsenic  is  present  as  arsenite  of  copj)er,  it  may  generally 
be  dissolved  ont  by  dilnte  nnimonia,  forming  ii  blue  solution,  which 
may  be  acidulated  with  hydrochloric  acid  and  examined  by  Keinsch's 
test.  This  method,  however,  is  not  applicable  in  all  cases,  even  when 
the  arsenic  exists  as  an  arsenite.  As  a  general  method.  Dr.  Hills 
advises  {Bostoii  Med.  and  Surg.  Jour.,  Jan.  1881,  29)  to  cut  the  ma- 
terial into  small  pieces,  moisten  it  with  pure  sulphuric  acid,  and  heat 
till  the  mass  is  thoroughly  charred.  The  ])ulverized  mass  is  extracted 
with  water,  the  liquid  filtered,  and  then  examined  by  Marsh's  test. 

Arsenic  in  Glass. — As  is  well  known,  arsenious  oxide  is  frequently 
emj)loyed  in  the  manufacture  of  glass,  it  being  added  chiefly  for  the 
purpose  of  oxidizing  any  iron  present  in  the  mixture  to  the  state  of 
ferric  oxide.  It  is  generally  believed,  and  so  stated  in  text-books, 
that  after  serving  this  purpose  the  arsenic  is  wholly  volatilized,  none 
of  it  remainino;  in  the  glass. 

Recently,  however,  Dr.  W.  Fresenius  found  arsenic  in  each  of 
three  kinds  of  glass  examined,  even,  in  a  sample  of  Bohemian  glass, 
to  the  extent  of  0.20  per  cent.  Moreover,  he  found  that  on  strongly 
heating  a  mixture  of  potassium  cyanide  and  sodium  carbonate  in  a 
current  of  carbon  dioxide,  according  to  the  method  of  Fresenius  and 
Babo,  in  a  tube  of  this  kind,  a  very  strong  arsenical  mirror  was  pro- 
duced, due  to  the  action  of  the  fused  mixture  upon  the  glass.  On 
placing  the  reducing  mixture  in  a  porcelain  boat,  so  as  to  prevent 
contact  with  the  glass,  and  repeating  the  experiment,  no  mirror  was 
obtained,  even  on  intense  and  prolonged  heating.  This  author 
believes  that  the  brown  coloration  sometimes  observed  in  the  glass  in 
the  application  of  Marsh's  test  is  due  to  the  presence  of  arsenic  in 
the  glass,  and  not,  as  is  generally  believed,  to  the  action  of  lead. 
{Zeits.  Anal.  Chem.,  1883,  397;  also,  Chem.  Neios,  Sept.  1883,  147.) 

Of  two  kinds  of  Bohemian  glass,  a  sample  of  bottle-glass,  and 
the  glass  of  a  beaker,  examined  in  the  University  laboratory  by 
Dr.  J.  Marshall  and  Mr.  C.  S.  Potts,  three  of  the  samples  were 
found  to  contain  notable  quantities  of  arsenic,  one  of  the  samples  of 
Bohemian  glass  being  entirely  free  from  the  metal.  The  arsenical 
Bohemian  glass  on  being  strongly  heated,  as  in  the  method  of  Marsh, 


320  ARSENIC. 

acquired  a  brown  coloration,  but  gave  no  mirror  whatever.  The 
other  sample  of  this  kind  of  glass  failed  to  yield  any  coloration. 
The  bottle-glass,  on  fusion,  was  found  to  contain  0.266  per  cent., 
and  the  arsenical  Bohemian  glass  0.314  per  cent.,  of  metallic  arsenic. 
The  bottle-glass  was  of  American  manufacture;  the  other  three 
kinds  examined  were  from  Thuringia.  One  gramme  of  a  porcelain 
dish  examined  for  arsenic  failed  to  yield  a  trace  of  the  metal. 

A  10  per  cent,  solution  of  sodium  hydrate,  kept  in  a  bottle  of  the 
above  arsenical  glass  and  examinetl  daily,  20  c.c.  at  a  time,  acquired 
a  distinct  arsenical  contamination  at  the  end  of  three  days.  Arsenic 
was  readily  detected  in  a  solution  of  this  kind  one  month  old ;  and 
the  quantity  was  much  increased  at  the  end  of  five  months.  It 
should  be  borne  in  mind  that  commercial  sodium  hydrate  may  itself 
be  contaminated  with  arsenic  [ante,  89) :  in  a  sample  of  the  hydrate 
claiming  to  be  chemically  pure  examined  in  our  own  laboratory  by 
Dr.  Marshall,  arsenic  was  present  to  the  extent  of  0.085  per  cent., 
calculated  as  arsenious  oxide;  and  in  another  sample  a  notable 
quantity  of  the  metal  was  present. 

A  10  per  cent,  solution  of  potassium  hydrate,  under  the  fore^ 
going  conditions,  acquired  a  perceptible  arsenical  contamination  in 
twenty-five  hours.  Solutions  of  ammonium  hydrate  and  ammonium 
sulphide,  and  of  various  neutral  reagents,  kept  in  bottles  of  arsenical 
glass  for  long  periods,  failed  to  take  up  a  trace  of  arsenic. 

From  the  foregoing  results  it  would  appear  that  there  would  be 
little  or  no  danger  of  arsenical  glass  yielding  up  any  of  the  metal 
in  the  ordinary  application  of  Marsh's  test.  Should  it  do  so,  this 
would  be  discovered  in  the  preliminary  examination  prior  to  the  ad- 
dition of  the  suspected  solution.  In  the  method  of  Fresenius  and 
Babo,  however, — unless  the  glass  was  previously  examined  and  found 
free  from  arsenic, — the  substance  with  the  reducing  mixture  should 
be  placed  in  a  porcelain  boat,  as  advised  by  Fresenius,  introduced 
into  the  tube  and  cautiously  dried  in  the  current  of  carbon  dioxide 
before  applying  a  strong  heat  to  the  mixture.  All  alkaline  solutions 
and  reagents  capable  of  acting  on  glass,  if  preserved  in  glass  bot- 
tles, should  be  carefully  examined  for  arsenic  before  being  employed 
in  an  analysis  for  this  metal.  The  mineral  acids  have  little  or  no 
action  upon  glass.  Samples  of  concentrated  sulphuric  and  hydro- 
chloric acids  that  had  been  in  bottles  of  strongly  arsenical  glass  for 
over  three  years  were  found  to  be  entirely  free  from  the  metal. 


QUANTITATIVE  ANALYSIS.  321 

Quantitative  Analysis. — Arsenic,  when  in  solution  in  the 
form  of  :irs(Miioiis  acid,  is  most  reiulily  cstiinated  as  arsenioiis  sul- 
phide. For  this  [)urpose  the  solution,  free  fn^n  organic  matter  and 
reducing  substances,  is  acidulated  with  hydrochloric  acid,  and  a  slow 
stream  of  washed  siilphiu'etted  hydrogen  gas  passed  through  it,  as 
long  as  a  preci{)itate  is  produced  ;  the  mixture  is  then  gently  heated, 
and  allowed  to  stand  in  a  moderately  warm  place  until  the  precipi- 
tate has  completely  subsided  and  the  supernatant  liquid  has  become 
perfectly  clear.  The  precipitate  is  collected  on  a  double  filter  (the 
two  filters  having  been  previously  equipoised),  and  well  washed,  at 
first  with  water  containing  a  little  sulphuretted  hydrogen,  then  dried 
at  100°  C.  (212°  F.).  The  filters  are  now  separated,  placed  on  the 
opposite  pans  of  the  balance,  and  tiie  excess  of  the  one  containing 
the  precipitate  determined. 

One  hundred  parts  by  weight  of  dry  arsenious  sulphide  corre- 
spond to  80.48  parts  of  pure  arsenious  oxide.  A  portion  of  the  dried 
precipitate,  heated  in  a  reduction-tube,  should  completely  volatilize, 
without  charring  or  leaving  any  residue;  otherwise  it  is  not  perfectly 
free  from  foreign  matter.  If  organic  matter  or  a  reducing  agent  be 
present  in  the  solution  treated  with  sulphuretted  hydrogen,  the  precipi- 
tate may  consist  largely,  or  even  wholly,  of  free  sulphur.  Hence  it  is 
very  important  to  determine  the  purity  of  the  precipitate,  especially 
when  the  absence  of  these  agents  has  not  been  fully  established. 

When  the  arsenic  exists  as  arsenic  acid,  it  may  be  estimated  as 
ammonium-magnesium  arsenate,  in  the  manner  directed  hereafter. 
By  this  method,  however,  the  results  are  slightly  too  low,  since  the 
precipitate  is  very  slightly  soluble  in  the  liquid  from  which  precipi- 
tated. Arsenious  acid  is  readily  converted  into  arsenic  acid  by  heat- 
ing the  hydrochloric  acid  solution  with  a  little  potassium  chlorate, 
and  maintaining  the  mixture  at  a  moderate  heat  until  the  odor  of 
chlorine  has  about  disappeared. 

The  weight  of  a  deposit  of  metallic  arsenic  obtained  in  the  reduc- 
tion-tube of  Marsh's  apparatus  may  be  determined  by  separating  the 
portion  of  the  tube  containing  the  deposit,  by  means  of  a  fine  file, 
and  weighing  it;  the  deposit  is  then  expelled  from  the  section  of 
tube  by  heat  or  dissolved  in  nitric  acid,  and  the  clean  and  dried  tube 
again  weighed,  when  the  loss  of  weight  will  represent  the  amount 
of  metallic  deposit  present.  One  part  of  metallic  arsenic  corre- 
sponds to  1.32  parts  of  arsenious  oxide. 

21 


322  AESENIC   OXIDE. — ARSENIC   ACID. 


3.  Arsenic  Oxide. — Arsenic  Acid. 

General  Chemical  Nature. — Arsenic  oxide,  or  arsenic  anhy- 
dride, known  also  as  anhydrous  arsenic  acid,  is  a  compound  of  two 
atoms  of  metallic  arsenic  with  five  atoms  of  oxygen,  AsgOg.  In 
its  pure  state  it  is  a  white,  odorless,  deliquescent  solid,  of  specific 
gravity  3.74.  When  exposed  to  a  red  heat,  arsenic  oxide  fuses  and 
is  slowly  dissipated,  being  resolved  into  arsenious  oxide  and  free 
oxygen  :  AsgOg  =  AS2O3  +  O^.  When  perfectly  dry,  arsenic  oxide  is 
only  slowly  soluble  in  water;  but  in  its  moist  state  it  is  very  readily 
soluble  in  this  menstruum. 

When  arsenic  oxide  dissolves  in  water,  one  molecule  of  the  oxide 
assimilates  the  elements  of  three  molecules  of  water,  forming  two 
molecules  of  arsem'c  acicZy  thus:  As205  +  3H20=:2H3As04.  Aque- 
ous solutions  of  arsenic  acid  are  colorless,  and  have  a  strongly  acid 
reaction,  quickly  reddening  litmus;  this  reaction  is  quite  distinct  in  a 
solution  containing  only  l-l  0,000th  of  its  weight  of  the  free  acid. 
When  an  aqueous  solution  of  arsenic  acid  is  treated  with  sulphurous 
oxide,  known  as  sulphurous  acid  gas,  the  arsenic  acid  is  reduced  to 
arsenious  acid,  and  the  sulphurous  oxide  oxidized  to  sulphuric  acid  : 
2H3ASO4+  2SO2  +  2H20=r  2H3ASO3  +  2H2SO,. 

Arsenic  acid,  like  common  phosphoric  acid,  is  tribasic,  either  one, 
two,  or  all  three  of  the  hydrogen  atoms  being  replaceable  by  a  metal. 
The  arsenates  of  the  alkalies  are,  for  the  most  part,  readily  soluble 
in  water;  the  other  metallic  arsenates  are  insoluble  in  water,  but 
soluble  in  sulphuric,  nitric,  and  hydrochloric  acids.  The  arsenates 
of  the  fixed  alkalies,  containing  two  or  three  equivalents  of  metal  for 
each  molecule  of  acid,  withstand  a  strong  red  heat  without  decompo- 
sition ;  but  when  they  contain  only  one  atom  of  metal,  they  are  re- 
duced to  the  bibasic  or  tribasic  form,  a  portion  of  the  acid  being 
decomposed  and  evolved  in  the  form  of  free  oxygen  and  arsenious 
oxide.  Under  the  action  of  heat  arsenic  acid  displaces  all  volatile 
acids  from  their  basic  combinations. 

In  regard  to  its  physiological  effects,  arsenic  oxide  appears,  from 
the  observations  of  several  experimentalists,  to  be  even  more  poison- 
ous than  arsenious  oxide.  As  yet,  however,  there  seems  to  be  no 
instance  of  poisoning  by  it  in  its  free  state  in  the  human  subject. 
But  several  instances  of  poisoning  by  potassium  arsenate  and  the 
sodium  salt  are  reported.      The  symptoms  observed  in  these  cases 


8ULPPIURETTED    HYDROGEN    TEST.  323 

were  iimcli  the  same  as  those  usually  produced  by  arsenious  oxide. 
The  treatment  and  post-mortem  appearances  are  also  much  the  same. 

Special  Chemical  Properties. — When  a  mixture  of  arsenic 
oxide  or  ot"  an  arsenate  and  sodium  carbonate  is  iieated  on  a  char- 
coal support,  in  the  inner  bh)w-pipe  flame,  the  arsenical  compound 
is  reduced  and  evolves  the  peculiar  garlic-like  odor  of  the  vaporized 
metal.  When  arsenic  oxide  or  any  of  its  compounds  is  intimately 
mixed  with  a  reducing  agent,  as  potassium  ferrocyanide,  and  the 
thoroughly  dried  mixture  heated  in  a  reduction-tube,  it  yields  a 
sublimate  of  metallic  arsenic,  similar  to  that  obtained  under  like 
circumstances  from  arsenious  oxide. 

When  a  drop  of  an  aqueous  solution  of  arsenic  acid  is  allowed  to 
evaporate  spontaneously,  the  residue  usually  consists  of  a  gummy 
mass ;  if,  however,  the  evaporation  has  taken  place  very  slowly,  the 
acid  is  left  chiefly  in  the  form  of  long,  slender,  crystalline  needles. 
This  residue  consists  of  two  molecules  of  the  acid  with  one  mole- 
cule of  water:  2H3ASO4;  H^.  At  100°  C.  (212°  F.)  the  water  of 
crystallization  is  expelled ;  and  at  a  heat  little  short  of  redness  the 
arsenic  acid  is  resolved  into  arsenic  oxide  and  water,  the  latter  being 
vaporized  :   2H3AsO^=  AsgOg  +  SHgO. 

If  the  aqueous  solution  residue  be  moistened  with  water  and  ex- 
posed to  sulphuretted  hydrogen  gas,  it  acquires  a  yellow  color,  due  to 
the  formation  of  sulphide  of  arsenic;  when  moistened  with  a  yellow 
solution  of  ammonium  sulphide  and  the  mixture  cautiously  evap- 
orated to  dryness,  it  leaves  a  pale  yellow  residue,  consisting  of  penta- 
sulphide  of  arsenic,  mixed  with  more  or  less  free  sulphur.  Silver 
nitrate  converts  the  arsenic  acid  residue  into  a  red-brown  deposit  of 
tribasic  silver  arsenate,  which  seems  to  have  a  tendency  to  crystallize. 
Under  this  action  of  silver  nitrate  the  1-lOOOth  of  a  grain  of  arsenic 
oxide  yields  a  very  good  red-brown  deposit,  and  l-10,000th  of  a 
grain  a  quite  distinct  reddish-brown  coloration. 

In  the  following^  examinations  in  reo^ard  to  the  behavior  of  solu- 
tions  of  arsenic  oxide,  pure  aqueous  solutions  of  the  free  acid  were 
employed. 

1.  Sulphuretted  Hydrogen. 

Normal  solutions  of  arsenic  acid,  even  when  highly  concentrated, 
fail  to  yield  an  immediate  precipitate  when  treated  with  sulphuretted 
hydrogen  gas ;  but  sooner  or  later  the  mixture  becomes  turbid,  and 
after  some  hours  yields  a  light  yellow  precipitate,  the  color  of  which 


324  AESENIC   OXIDE. — AESENIC   ACID. 

is  much  lighter  than  that  of  the  precipitate  produced  from  solutions 
of  arsenious  acid.  From  solutions  acidulated  with  hydrochloric  acid 
the  precipitate  separates  more  promptly,  but  even  under  these  con- 
ditions there  is  no  immediate  deposit.  The  precipitate,  according  to 
Wackenroder,  consists  of  a  mixture  of  free  sulphur  and  arsenious 
sulphide,  the  sulphuretted  hydrogen  first  reducing  the  arsenic  acid  to 
arsenious  acid,  and  the  latter  then  being  decomposed  and  the  metal 
precipitated  as  trisulphide  :  2H3ASO4  -[-  SHgS  =  SHgO  -f-  Sg  +  AsgS,. 
The  formation  of  the  precipitate  is  much  facilitated  by  a  gentle  heat. 

The  precipitate  thus  produced  is  insoluble  in  hydrochloric  acid, 
but  readily  soluble  to  a  clear  and  colorless  solution  in  aqua  ammonias, 
as  well  as  in  the  sulphides  and  carbonates  of  that  alkali.  It  is  also 
soluble  in  the  fixed  caustic  alkalies,  and  in  their  carbonates  and  sul- 
phides; the  fixed  alkalies  and  their  carbonates,  however,  leave  a  little 
free  sulphur  undissolved,  which  imparts  to  the  solution  a  slight 
turbidity.  If  either  of  these  solvent  substances  be  present  in  the 
solution,  the  reagent  will,  of  course,  fail  to  produce  a  precipitate. 

In  the  following  experiments  in  regard  to  the  limit  of  this  test, 
ten  fluid-grains  of  the  arsenical  solution,  placed  in  a  small  test-tube, 
were  acidulated  with  two  drops  of  concentrated  hydrochloric  acid, 
and  treated  with  a  slow  stream  of  washed  sulphuretted  hydrogen  gas. 

1.  1-lOOth  solution  (=3^  grain  of  arsenic  oxide)  yields  no  imme- 

diate change,  but  in  about  five  minutes  the  solution  becomes 
slightly  turbid,  and  in  about  five  minutes  more  a  strong,  yellow 
turbidity  appears  ;  if  the  mixture  be  now  allowed  to  stand  for 
a  few  hours,  a  quite  copious,  pale  yellow  precipitate  separates. 

A  similar  quantity  of  a  normal  solution  of  the  acid,  when 
treated  with  the  reagent,  becomes  turbid  in  about  the  same  time 
as  an  acidulated  solution,  but  fails  to  yield  a  precipitate,  even 
after  standing  many  hours. 

2.  1-lOOOth  solution,  when  saturated  with  the  sulphuretted  gas, 

undergoes  no  perceptible  change  for  about  half  an  hour ;  the 
liquid  then  becomes  turbid,  and  after  several  hours  lets  fall  a 
good  precipitate. 

3.  1-1 0,000th  solution:  no  perceptible  change  for  some  hours;  after 

about  eighteen  hours  a  quite  perceptible,  yellowish  precipitate 
has  formed. 
The  arsenical  nature  of  the  precipitate  produced  by  this  reagent 
may  be  established  by  either  of  the  following  methods,     a.  When 


AMMONIO  COPPER  SULPHATE  TEST.  325 

tlie  precipitate  is  boiled  with  diluted  hydrochloric  acid  and  a  slip  of 
bright  copper-foil,  the  latter  slowly  receives  a  coatiiif;  of  metallic 
arsenic,  h.  If  the  j)recipitate  be  thoroughly  dried  and  heated  in  a 
reduction-tube,  it  first  fuses,  then  wholly  volatilizes,  yielding  a  viscid 
globular  sublimate.  The  lower  margin  of  this  sublimate,  while  still 
warm,  has  a  dark  color,  while  the  central  portion  appears  red,  and 
the  upper  margin  yellow;  when  cool,  the  whole  of  the  sublimate 
assumes  a  yellow  color,  which  in  the  upper  portion  of  the  deposit  is 
quite  pale.  c.  When  dried  and  heated  in  a  reduction-tube,  with  a 
mixture  of  potassium  cyanide  and  sodium  carbonate,  or  with  potas- 
sium ferrocyanide,  it  yields  a  sublimate  of  metallic  arsenic. 

On  comparing  the  above  results,  o])tained  from  solutions  of 
arsenic  oxide  by  sulphuretted  hydrogen,  with  those  obtained  from 
solutions  of  arsenious  oxide  {ante,  265),  it  is  obvious  that  the  former 
oxide  is  much  more  slowly  and  less  completely  precipitated  by  the 
reagent  than  the  latter.  When,  therefore,  the  poison  exists  in  solution 
in  the  form  of  arsenic  acid,  before  applying  the  reagent  it  should  be 
reduced  to  arsenious  acid,  by  saturating  the  solution  with  sulphurous 
oxide,  and  gently  heating  the  liquid  until  the  odor  of  the  gas  has 
entirely  disappeared. 

2.  Ammonio  Copper  Sulphate. 

This  reagent  produces  in  normal  solutions  of  arsenic  acid  a 
greenish-blue,  amorphous  precipitate  of  copper  arsenate,  CuHAsO^. 
The  same  precipitate  is  produced  from  solutions  of  neutral  arsenates 
by  copper  sulphate  alone,  but  this  reagent  fails  to  produce  a  precipi- 
tate in  solutions  of  the  free  acid.  The  precipitate  is  readily  soluble 
in  nitric  acid  and  in  ammonia,  also  in  excess  of  free  arsenic  acid. 
In  its  general  deportment  with  reagents  it  is  very  similar  to  the 
corresponding  precipitate  produced  from  arsenious  acid. 

1.  _^  grain  of  arsenic  oxide,  in  one  grain  of  water,  yields  with  the 

reagent  a  copious,  greenish-blue  precipitate,  which  after  a  time 
assumes  a  more  distinctly  green  tint.  Ten  grains  of  the  solu- 
tion yield  a  bluish-green  precipitate,  which  after  a  little  time 
acquires  a  green  color. 

2.  -A—,  grain :  a  good,  bluish  precipitate,  destitute  of  a  green  tint. 

The  precipitate  from  ten  grains  of  the  solution  has  a  distinct 
greenish  hue,  which  after  a  time  becomes  well  marked. 
This  test,  like  the  preceding,  is  much  less  satisfactory  and  deli- 


326  ARSENIC   OXIDE. — ARSENIC   ACID. 

cate  when   applied  to  solutions  of  arsenic   acid   than  to  those  of 
arsenious  acid. 

3.  Silver  Nitrate. 

Silver  nitrate  throws  down  from  normal  and  neutral  solutions  of 
arsenic  acid,  when  not  too  dilute,  a  reddish-brown  precipitate  of 
tribasic  silver  arsenate,  AggAsO^.  The  precipitate  is  readily  soluble 
in  nitric  acid,  but  nearly  wholly  insoluble  in  acetic  acid  ;  it  is  also 
freely  soluble  in  ammonia,  and  sparingly  soluble  in  ammonium 
carbonate  and  nitrate. 

1.  YFo"  gi'si'^  of  arsenic  oxide,  in  one  grain  of  water,  yields  a  quite 

copious  precipitate,  which  aggregates  into  little  masses,  with  a 
tendency  to  crystallize. 

2.  YWoo  E^^^^ '  ^  copious,  reddish-brown  precipitate. 

3.  Yo'.^To  g^^^i^i  yields  a  dirty-white  precipitate,  which  after  a  time 

assumes   a   reddish-brown   tint.       Ten  grains  of  the  solution 
yield   a   dirty  reddish-brown  precipitate,  which  after  a  time 
acquires  a  clear  reddish-brown  color. 
The  production  of  a  reddish-brown  precipitate  by  this  reagent 
is  quite  peculiar  to  arsenic  acid. 

Ammonio  silver  nitrate  produces,  in  solutions  of  arsenic  acid, 
much  the  same  results  as  the  silver  salt  alone,  as  above  described. 

4.  ReinscKs  Test. 

When  a  solution  of  arsenic  acid  or  of  an  arsenate  is  strongly 
acidulated  with  hydrochloric  acid  and  boiled  with  a  slip  of  bright 
copper-foil,  metallic  arsenic  is  slowly  deposited  upon  the  copper, 
forming  an  iron-gray  or  steel-like  coating,  the  appearance  depending 
on  the  thickness  of  the  deposit.  Without  the  addition  of  the  hy- 
drochloric  acid  the  metallic  deposit  fails  to  appear.  The  arsenical 
nature  of  the  deposit  may,  of  course,  be  shown  in  the  same  manner 
as  heretofore  pointed  out  in  the  consideration  of  this  test  for  the 
detection  of  arsenious  acid. 

1.  YFo  gi'^iij^  of  arsenic  oxide,  in  one  grain  of  water,  when  acidulated 

with  hydrochloric  acid,  and  heated  to  about  the  boiling  temper- 
ature with  a  mere  fragment  of  copper-foil,  yields,  after  a  time, 
a  very  good  metallic  deposit  upon  the  copper. 

2.  YWWQ  gi'^iii  •  after  a  time  a  quite  good  deposit. 

3.  xo".ToT  gJ^ain   imparts  only  a  slight  tarnish  to  the  copper,  even 


AMMONIUM    MAGNESIUM    SULPHATE   TEST.  327 

after  prolonged  heating,  the  evaporated  liquid  being  frequently 

renewed. 
It  will  be  observed,  on  comparing  the  above  results  with  those 
obtained  from  solutions  of  arsenious  oxide,  that  the  metal  is  much 
less  completely  separated  by  the  test  from  solutions  of  arsenic  oxide 
than  from  arsenious  oxide. 

5.  Ammonium  Magnesium  Sulphate. 

This  reagent  may  be  prepared  by  precipitating  a  solution  of  pure 
niao-ncsium  sulphate  by  ammonia,  and  then  adding  sufficient  ammo- 
nium chloride  to  redissolve  the  precipitate;  or,  according  to  Fresenius, 
by  dissolving  one  part  of  crystallized  magnesium  sulphate  and  one 
part  of  ammonium  chloride  in  eight  parts  of  water  and  four  parts 
of  solution  of  ammonia,  allowing  the  mixture  to  stand  at  rest  for 
some  days,  and  then  filtering. 

Solutions  of  free  arsenic  acid,  and  of  neutral  arsenates,  yield 
with  the  reagent  a  white,  crystalline  precipitate  of  ammonium  mag- 
nesium arsenate,  which  contains  six  molecules  of  water  of  crystalli- 
zation, the  formula  being  MgNH^AsO^GH^O.  The  precipitate  is 
readilv  soluble  in  nitric,  hydrochloric,  and  acetic  acids,  also  in  excess 
of  free  arsenic  acid,  but  only  very  sparingly  soluble  in  ammonia 
and  in  ammonium  chloride.  The  reagent  fails  to  produce  a  precipi- 
tate in  solutions  of  arsenious  oxide. 

1.  _i^  grain  of  arsenic  oxide,  in  one  grain  of  water,  yields  a  copious, 

white,  amorphous  precipitate,  which  immediately  begins  to 
crystallize,  and  in  a  little  time  becomes  converted  into  a  mass 
of  plumose  crystals,  Plate  V.,  fig.  1. 

2.  -j-^  grain :  no  direct  precipitate,  but  almost  immediately  crys- 

tals begin  to  separate,  and  very  soon  there  is  a  copious  deposit 
of  crystals,  having  much  the  same  forms  as  those  illustrated 
under  1. 

3.  ^^1^^  grain:  almost  immediately  a  granular  cloudiness  appears, 

followed  in  a  little  time  by  crystals;  after  several  minutes  there 
is  a  quite  good  crystalline  deposit. 

4.  -j^  i^pg-  grain  :  in  a  very  little  time  a  granular  turbidity,  and  after 

some  minutes  a  satisfactory  precipitate,  consisting  principally 
of  small  crystalline  plates. 
The  reagent  also  produces  a  similar  crystalline  precipitate  in  solu- 
tions of  phosphoric  acid.     The  true  nature  of  the  arsenical  crystals 


328  AESENIC   OXIDE. — ARSEJSTIC   ACID. 

may  be  readily  established  by  dissolving  the  precipitate  in  large 
excess  of  hydrochloric  acid  and  boiling  the  solution  with  a  slip  of 
bright  copper-foil,  when  the  latter  will  receive  a  coating  of  metallic 
arsenic. 

Lead  acetate  throws  down  from  solutions  of  free  arsenic  acid 
and  of  alkaline  arsenates  a  white,  curdy  precipitate  of  tribasic  lead 
arsenate,  Pb32As04.  One  grain  of  a  1-lOOth  solution  of  the  oxide 
yields  a  quite  copious  precipitate;  the  same  quantity  of  a  1— 1000th 
solution  yields  a  very  good  precipitate ;  and  a  l-10,000th  solution 
becomes  quite  turbid.  It  need  hardly  be  remarked  that  this  reagent 
also  produces  white  precipitates  in  solutions  of  many  other  acids. 

Under  the  action  of  zinc  and  diluted  sulphuric  acid,  in  a  Marsh's 
apparatus,  arsenic  acid  undergoes  decomposition,  with  the  production 
of  arsenuretted  hydrogen,  much  in  the  same  manner  as  arsenious 
acid. 

Solutions  of  arsenic  acid,  unlike  those  of  arsenious  acid,  fail  to 
reduce  acid  potassium  chromate ;  nor  do  they  give  rise  to  red  copper 
suboxide,  when  boiled  with  caustic  potash  and  copper  sulphate. 

Quantitative  Analysis. — Arsenic  oxide,  when  in  solution, 
may  be  estimated  in  the  form  of  ammonium  magnesium  arsenate. 
The  solution  is  treated  with  excess  of  a  clear  mixture  of  magnesium 
sulphate,  ammonia,  and  ammonium  chloride,  prepared  in  the  manner 
already  described,  and  then  allowed  to  stand  in  a  cool  place  for  from 
twelve  to  twenty-four  hours,  in  order  that  the  precipitate  may  com- 
pletely separate.  The  precipitate  is  then  collected  on  a  filter  of 
known  weight,  washed  with  water  containing  a  little  ammonia,  dried 
at  100°  C.  (212°  F.)  as  long  as  it  loses  in  weight,  and  its  weight 
then  noted.  The  dried  precipitate,  if  pure,  will  now  consist  of 
2MgNH^As04;  H2O,  every  100  parts  of  which,  by  weight,  corre- 
spond to  60.53  parts  of  arsenic  oxide,  52.1  of  arsenious  oxide,  or 
39.47  of  metallic  arsenic. 

Instead  of  drying  the  precipitate  until  it  is  constant  in  weight, 
in  the  manner  just  directed,  it  may  be  carefully  transferred  from  the 
filter  to  a  small  weighed  porcelain  crucible  and  then  ignited ;  the 
filter  is  burned  separately,  the  ash  added  to  the  cooled  contents  of  the 
crucible,  and  the  whole  moistened  with  nitric  acid  and  again  heated  to 
redness.     The  precipitate  will   thus  be  converted   into   magnesium 


QUANTITATIVE   ANALYSIS.  329 

jyyi'o-ar senate,   wliicli  lias  tlu-  composition  Mg.^AsjOy,  and  contains 
48.38  per  cent,  of  metallic  arsenic. 

Arsenic  oxide  may  also  be  estimated  by  first  redncing  it  to  ar- 
senious  oxide,  by  means  of  sulplinrons  oxide,  and  then  precipitating 
the  metal  as  arsenious  sulphide,  by  sulphuretted  hydrogen.  One 
hundred  parts  by  weight  of  thoroughly  dried  arsenious  sulphide 
correspond  to  93.5  parts  of  anhydrous  arsenic  oxide. 


330  MERCURY. 


CHAPTER  TL 

MERCURY. 

Properties. — In  its  uncombined  state,  at  ordinary  temperatures, 
mercury,  or  quicksilver,  as  it  has  been  named,  is  a  liquid  metal  having 
a  silver- white  color,  high  metallic  lustre,  and  a  density  of  13.595; 
its  atomic  weight  is  200.  Mercury  is  the  only  metal  that  is  fluid  at 
ordinary  temperatures.  At  — 39.4°  C.  ( — 39.6°  F.)  it  solidifies  to  a 
crystalline,  ductile  mass;  and  at  about  350°  C.  (662°  F.)  it  boils, 
being  dissipated  in  the  form  of  a  colorless,  transparent  vapor,  the 
specific  gravity  of  which  is  6.976.  Water  has  no  action  on  the 
metal  in  its  pure  state.  Diluted  nitric  acid  dissolves  it  to  mercurous 
nitrate;  the  hot  concentrated  acid  readily  dissolves  it  to  mercuric 
nitrate,  with  evolution  of  nitrous  fumes.  Hydrochloric  acid  has 
no  action  upon  the  metal,  but  boiling  sulphuric  acid  readily  con- 
verts it  into  mercuric  sulphate,  with  evolution  of  sulphuroas  oxide. 

Physiological  Effects. — Many  instances  are  reported  in  which  large 
quantities  of  metallic  mercury,  even  in  some  instances  amounting  to 
some  pounds,  were  taken  into  the  body  without  producing  any  dele- 
terious effects.  If,  however,  the  metal,  after  being  swallowed,  becomes 
oxidized,  as  is  sometimes  the  case,  it  may  produce  active  symptoms. 
A  case  in  which  about  four  ounces  and  a  half  of  quicksilver,  given 
to  procure  abortion,  produced  serious  symptoms,  has  been  reported 
by  Sir  G.  Duncan  Gibb.  {Amer.  Jour' Med.  Scl,  July,  1873,  280.) 
"When  inhaled  in  the  form  of  vapor,  mercury  may  give  rise  to  serious 
results,  as  has  not  unfrequently  been  witnessed  in  those  engaged  in 
mining  the  metal,  and  others  exposed  to  its  fumes.  In  a  case  of  this 
kind  reported  by  M.  Ferrand,  a  woman  exposed  to  the  fumes 
experienced  violent  effects,  which  continued  for  a  month  or  longer. 
(Med.-Chir.  Rev.,  April,  1869,  547.) 

Combinations. — Mercury  readily  unites  with  most  of  the  non- 


PHYSIOLOGICAL    EFFECTS.  331 

metallic  elements.  With  oxygen  it  combines  in  two  proportions, 
forming  the  black,  or  suboxide,  known  also  as  mercurous  oxide, 
Hg.,0,  and  the  monoxide,  red  oxide,  or  mercuric  oxide,  HgO.  These 
oxides  readily  unite  with  acids,  forming  salts.  The  metal  also  unites 
with  sulphur  in  two  corresponding  proportions:  the  subsulphide, 
Hg.S,  has  a  black  color,  so  also  has  the  monosulphide,  HgS  ;  by  sub- 
limation the  latter  comi)ound  acquires  a  beautiful  red  color,  under 
which  form  it  is  commonly  known  as  vermilion.  Mercurous  iodide, 
HiT.Jj,  has  a  dingy  green  color,  while  mercuric  iodide,  Hglj,  has  a 
brilliant  scarlet  hue.  The  compounds  of  mercury  most  frequently 
employed  for  medicinal  purposes  are  the  two  chlorides,  known  at 
present  as  mercurous  chloride,  or  calomel,  HggClg,  and  mercuric 
€hloride,  or  corrosive  sublimate,  HgCU. 

All  the  compounds  of  mercury  are  more  or  less  poisonous  ;  but  of 
the.se,  corrosive  sublimate  is  one  of  the  most  active,  and,  in  a  medico- 
legal point  of  view,  much  the  most  important. 

Corrosive  Sublimate. 

Composition. —  Corrosive  sublimate  consists  of  one  atom  of  mer- 
cury combined  with  two  atoms  of  chlorine,  its  formula  being  HgClg. 
Some  confusion  has  existed  in  regard  to  the  nomenclature  of  the 
chlorides  of  mercury,  since  formerly  the  atomic  weight  of  the  metal 
was  assumed  to  be  100,  whereas  at  present  it  is  regarded  as  200. 
As  met  with  in  the  shops,  corrosive  sublimate  is  usually  either  in  the 
form  of  a  white,  amorphous  powder,  or  of  semi-transparent  crystal- 
line masses ;  but  occasionally  it  is  found  in  the  form  of  well-defined 
crystals. 

Symptoms. — The  effects  of  corrosive  sublimate,  when  swallowed 
in  poisonous  quantity,  are  a  nauseous,  metallic  taste,  with  a  sense  of 
heat  and  constViction  in  the  mouth  and  throat;  nausea,  and  pain  in 
the  stomach,  attended  with  violent  vomiting  and  retching,  the  matters 
ejected  being  sometimes  of  a  bilious  character  and  containing  blood; 
pain  throughout  the  abdomen,  which  generally  becomes  swollen  and 
tender  to  the  touch ;  severe  purging,  sometimes  of  bloody  matters ; 
great  anxiety;  flushed  countenance ;  impaired  or  difiScult  respiration  ; 
small,  frequent,  and  contracted  pulse;  cold  perspirations;  intense 
thirst;  scantiness  or  entire  suppression  of  urine;  cramps  in  the 
extremities;  stupor;  and  sometimes  death  is  ushered  in  with  con- 
vulsions. 


332  MERCURY. 

Such  are  the  symptoms  usually  produced  by  large  doses  of  this 
poison;  but  they  are  subject  to  considerable  variation.  The  vomit- 
ing and  purging,  as  well  as  the  pain  in  the  stomach  and  bowels,  may 
cease  for  a  time,  and  afterward  return  with  increased  violence.  In- 
stances are  also  reported  in  which  purging  and  pain  in  the  abdomen 
were  even  entirelv  wanting.  In  some  instances,  on  account  of  the 
local  action  of  the  poison,  the  lining  membrane  of  the  mouth  and 
the  surface  of  the  tongue  present  a  white  appearance.  In  protracted 
cases,  inflammation  of  the  mouth  and  salivation  usually  supervene. 

Among  the  more  prominent  differences  usually  observed  between 
the  symptoms  of  corrosive  sublimate  poisoning  and  those  occasioned 
by  arsenious  acid.  Dr.  Christison  mentions  the  following  :  1.  The 
symptoms  of  the  former  generally  begin  much  sooner,  the  irritation 
in  the  throat  often  manifesting  itself  during  the  act  of  swallowing, 
and  that  in  the  stomach  either  immediately  or  within  a  few  minutes ; 
2.  Its  taste  is  much  more  unequivocal  and  strong ;  3.  The  sense  of 
acridity  along  the  throat  and  in  the  stomach  is  much  more  severe; 
and,  4.  Blood  is  more  frequently  discharged  by  vomiting  and  purging. 

The  following  case,  related  by  Devergie  and  quoted  by  Dr.  ChrLs- 
tison,  well  illustrates  the  usual  course  of  acute  poisoning  by  this 
substance.  A  woman  swallowed  three  drachms  of  corrosive  subli- 
mate in  solution.  She  was  soon  afterward  seized  with  vomiting,, 
purging,  and  pain  in  the  abdomen.  In  five  hours  the  skin  was  cold 
and  clammy,  the  limbs  relaxed,  the  face  pale,  eyes  dull,  and  the 
expression  that  of  horror  and  anxiety.  The  lips  and  tongue  were 
white  and  shrivelled,  and  there  were  violent  fits  of  pain  and  spasm 
in  the  throat  whenever  an  attempt  was  made  to  swallow  liquids; 
also  burning  and  pricking  along  the  gullet ;  frequent  vomiting  of 
mucus  and  bilious  matters,  with  burning  pain  in  the  stomach  and 
tenderness  of  the  epigastrium  on  the  slightest  pressure;  and  profuse 
purging,  with  tenesmus.  The  pulse  was  almost  imperceptible,  and 
the  breathing  much  retarded.  In  eighteen  hours,  these  symptoms- 
still  continued  without  any  material  change;  but  the  limbs  were 
then  insensible.  In  twenty-three  hours,  the  patient  died  in  a  fit  of 
fainting,  the  mind  having  remained  clear  up  to  the  time  of  death. 

In  a  case  reported  by  Dr.  J.  W.  Ogle  {St.  George^s  Hosp.  Rep., 
1868,  238),  a  man  of  intemperate  habits  swallowed  a  tablespoonful, 
it  was  said,  of  corrosive  sublimate  in  a  cup  of  vinegar.  Within  an 
hour  after  taking  the  poison  the  patient  began  to  suffer  severe  pain 


PHYSIOLOGICAL    EFFECTTS. 


333 


in  llic  ccsophagus  and  epigastric  region  ;  and  there  was  vomiting  and 
purging,  the  matters  vomited  and  passed  by  the  bowels  being  mixed 
witii  bh)od.  When  admitted  to  the  liospiUil,  his  face  was  of  a  dusky 
leaden  color;  the  expression  very  anxious;  and  there  were  tremors 
of  the  lips  and  limbs.  There  was  no  pulse,  the  skin  was  cold,  and 
articulation  was  difficult.  The  vomiting  and  purging  continued.  On 
the  following  day  he  was  better,  the  purging  was  less,  and  there  was 
no  pain ;  the  pulse  had  become  natural.  Later,  however,  hiccough 
supervened,  and  the  purging  returned.  Collapse  set  in,  and  the 
patient  died  sixty  houi-s  after  taking  the  poison.  Dr.  Ogle  relates 
another  case  in  which  about  two  drachms  of  the  poison  proved  fatal 
on  the  sixth  day.  In  this  instance  there  was  a  paralytic  condition 
of  the  upper  eyelid  (ptosis)  and  facial  paralysis. 

Dr.  H.  M.  Post,  of  St.  Louis,  reports  a  case  in  which  sixty  grains 
of  the  poison  were  given  by  mistake  to  a  young  woman  convalescing 
from  intermittent  fever.  {Boston  lied,  and  Surg.  Jour.,  Nov.  1879, 
78L)  Although  there  was  speedy  and  free  vomiting,  this  was  con- 
tinued by  the  administration  of  large  quantities  of  milk  and  an 
emetic.  Some  three  or  four  hours  after  the  poison  was  given  there 
was  an  abundant  discharge  of  urine,  and  several  evacuations  from 
the  bowels.  The  patient  suffered  little  pain,  and  the  following  day 
her  recovery  seemed  almost  certain.  The  third  day,  however,  she 
was  very  weak,  vomiting  recurred,  and  she  seemed  sinking.  The 
symptoms  were  suppression  of  the  urine,  insomnia,  and  loss  of 
appetite ;  only  after  some  days  was  any  abdominal  tenderness  de- 
veloped. On  the  evening  of  the  sixth  day  the  patient  died  in 
convulsions. 

In  a  very  protracted  case,  reported  by  Dr.  Yigla,  the  following 
symptoms  were  observed.  A  man,  aged  twenty-seven  years,  swal- 
lowed, in  a  state  of  solution,  about  fifty  grains  of  corrosive  subli- 
mate. At  once  there  occurred  a  strong  metallic  taste,  constriction 
of  the  throat,  nausea,  and  vomiting;  but  no  severe  pain.  The 
vomited  matters  at  first  consisted  of  food,  then  of  a  serous  fluid. 
An  emetic  was  administered,  and  afterward  milk  and  white  of  egg. 
On  the  following  day  there  was  more  intense  pain  and  irritation  of 
the  throat,  coming  on  in  paroxysms ;  convulsive  cough,  expectoration 
of  bloody  mucus,  and  much  suffering.  Enteritis  also  developed  itself, 
with  violent  colic,  tenesmus,  and  frequent  slimy  and  bloody  evacua- 
tions.    On  the  third  day  there  was  great  inflammation  of  the  mucous 


334  MEECURY. 

membrane  of  the  throat  and  mouth,  oedema  of  the  palate  and  gullet, 
pseudo-membranous  separation  from  the  inflamed  parts,  and  saliva- 
tion ;  the  intelligence  was  somewhat  restored.  The  pulse  was  eighty- 
six;  the  urine  normal.  Up  to  the  twelfth  day,  all  inflammatory 
symptoms  gradually  subsided ;  but  from  that  time  great  prostration 
of  the  powers  of  life  and  mercurial  cachexia  were  presented.  On 
the  fifteenth  day,  ecchymosis  upon  the  skin,  irregular  action  of  the 
heart,  hiccough,  albuminuria,  and  great  irritability  of  the  whole  body 
were  present.  The  man  died  on  the  sixteenth  day,  without  any  con- 
vulsion or  struggle,  in  a  state  of  extreme  exhaustion.  {Med.-Chir. 
Rev.,  Oct.  1860,  380.) 

In  poisoning  by  frequently  repeated  small  doses  of  corrosive  sub- 
limate, or  chronio  poisoning,  as  it  is  termed,  the  following  symptoms 
are  usually  observed :  a  coppery  taste  in  the  mouth,  loss  of  appetite, 
offensive  breath,  tenderness  of  the  gums,  pains  in  the  stomach  and 
bowels,  nausea,  inflammation  and  ulceration  of  the  salivary  glands, 
swelling  of  the  tongue,  increased  flow  of  saliva,  hot  skin,  quick  pulse, 
and  great  muscular  debility.  It  is  well  known  that  some  persons 
are  much  more  susceptible  than  others  to  the  action  of  mercurial 
compounds.  In  a  case  cited  by  Dr.  Christison,  two  grains  of  calomel 
caused  ptyalism,  extensive  ulceration  of  the  throat,  exfoliation  of  the 
lower  jaw,  and  death. 

The  external  application  of  corrosive  sublimate  has  not  unfre- 
quently  been  followed  by  fatal  results.  Two  children,  aged  seven 
and  eleven  years  respectively,  had  an  ointment  composed  of  one  part 
of  corrosive  sublimate  to  four  parts  of  tallow  rubbed  over  the  scalp, 
for  the  cure  of  scald-head.  Extreme  suffering  almost  immediately 
ensued,  and  in  forty  minutes  they  were  completely  delirious.  There 
was  excessive  vomiting,  great  pain  in  the  bowels,  with  purging  and 
bloody  stools,  and,  in  one  instance,  complete  suppression  of  urine : 
there  was  no  ptyalism.  Death  ensued  in  one  instance  on  the  seventh, 
and  in  the  other  on  the  ninth,  day.  (Wharton  and  Still6,  Med.  Jur., 
535.)  In  an  instance  quoted  by  Orfila,  the  application  of  powdered 
corrosive  sublimate  to  the  breast  of  a  woman  aff^ected  with  an  ulcer- 
ated cancer  caused  intense  pain  in  the  part,  nausea,  bloody  vomiting, 
convulsions,  and  death  on  the  following  morning. 

Dr.  Leiblinger  relates  an  instance  in  which  three  persons  were 
found  dead  in  their  beds  who  some  days  before  rubbed  their  bodies 
over  with  an  ointment  made  from  quicksilver,  as  a  cure  for  itch. 


FATAL    PERIOD.  335 

Chemical  analyses  of  the  visceral  origans  of  i\w.  bodies  showed  the 
presence  of  large  quantities  of  mercury.  {Med.-Chir.  Rev.,  Jan. 
1872,  270.) 

Period  when  Fatal. — The  fatal  period  in  acute  poisoning  by 
corrosive  sublimate  is  subject  to  considerable  variation  ;  but  on  an 
average,  perhaps,  death  takes  place  in  about  twenty-four  hours.  In 
an  instance  in  which  three  children  were  accidentally  poisoned  by 
this  substance,  dispensed  by  mistake  for  calomel,  the  eldest,  aged 
seven  years,  took  eighteen  grains,  and  died  in  three  hours;  the 
youngest,  aged  about  two  years,  took  six  grains,  and  died  in  eleven 
hours;  while  the  second,  aged  three  years,  received  twelve  grains, 
and  apparently  recovered  from  the  immediate  effects  of  the  poison, 
but  died  with  secondary  symptoms  on  the  twenty-third  day.  {Med.- 
Chir.  Rev.,  April,  1835.)  In  a  case  recorded  by  Dr.  Taylor  {On 
Poisons,  462),  a  man  died  from  the  effects  of  an  unknown  quantity 
of  the  poison  in  less  than  half  an  hour.  This  is  the  most  rapidly 
fatal  case  yet  reported. 

In  regard  to  protracted  cases,  Dr.  Beck  cites  an  instance  in  which 
death  did  not  occur  until  the  eighth  day ;  and  another  in  which  a 
man  took  about  six  or  eight  grains  of  the  poison,  and  life  was  pro- 
longed until  the  twelfth  day.  {3Ied.  Jur.,  ii.  620.)  In  a  case  re- 
ported by  Dr.  Coale,  death  took  place  on  the  eleventh  day ;  and  in 
another,  by  Dr.  Jackson,  on  the  thirteenth  day.  (Wharton  and 
Stille,  Med.  Jur.,  534.)  In  Dr.  Vigla's  case,  already  cited,  death 
was  delayed  until  the  sixteenth  day. 

Fatal  Quantity. — That  the  same  effects  are  not  always  produced 
by  equal  quantities  of  corrosive  sublimate  is  well  illustrated  in  the 
cases  of  the  three  children  just  cited,  in  one  of  whom  six  grains  of 
the  poison  caused  death  in  eleven  hours,  whilst  in  another  twelve 
grains  did  not  prove  fatal  until  the  twenty-third  day.  In  Dr.  Coale's 
case,  ten  grains  of  the  poison,  dispensed  by  mistake  for  calomel,  "  w'ere 
mixed  and  partially  swallowed,  but  the  great  distress  it  caused  pro- 
duced ejection  of  much  of  it  from  the  stomach."  {Amei'.  Jour.  Med. 
Sci.,  Jan.  1851,  47.)  This  case  is  also  remarkable  in  that  during 
the  eleven  days  the  man  survived  after  taking  the  dose  there  was 
entire  suppression  of  urine.  A  case  has  also  just  been  cited  in  which 
six  or  eight  grains  proved  fatal  to  an  adult. 

Dr.  Kobryner  reports  a  case  in  which  a  young  man  under  treat- 
ment for  syphilis  took  one-third  of  a  grain  of  corrosive  sublimate  in 


336  MERCURY. 

two  pills.  He  soon  experienced  intolerable  burning  pain  in  the 
stomach  and  abdomen,  and  vomiting.  His  pulse  became  small, 
the  extremities  cold,  and  his  face  pinched.  After  ten  hours,  the 
symptoms  began  to  diminish,  the  patient  finally  recovering.  [Med. 
Times,  Phila.,  Xov.  1878,  60.) 

On  the  other  hand,  several  instances  are  reported  in  which  per- 
sons recovered  after  having  taken  from  half  a  drachm  to  two  drachms 
of  the  poison ;  and  Dr.  Beck  quotes  an  instance  in  which  recovery 
took  place  after  six  drachms,  in  solution,  had  been  swallowed.  The 
writer  just  mentioned  also  cites  a  case,  reported  by  Dr.  Budd,  in 
which  a  female  took  an  ounce  of  the  poison,  and,  after  suffering  the 
usual  severe  symptoms,  entirely  recovered.  So,  also.  Dr.  Taylor  cites 
an  instance  mentioned  by  Dr.  Booth,  in  which  recovery  followed 
after  a  similar  quantity  had  been  taken.  It  is  but  proper  to  add 
that  in  most,  if  not  in  all,  of  these  cases  of  recovery  there  was 
early  vomiting. 

Treatment. — Of  the  various  antidotes  that  have  been  proposed 
in  poisoning  by  corrosive  sublimate,  albumen,  in  the  form  of  white 
of  egg,  seems  to  be  much  the  most  eflScient.  Orfila,  who  first  sug- 
gested this  antidote,  employed  it  with  complete  success  in  experiments 
on  poisoned  animals ;  and  it  has  in  several  instances  been,  at  least 
apparently,  the  means  of  saving  life  in  the  human  subject.  It  should 
be  given  in  large  quantity,  and  its  administration  speedily  followed, 
if  necessary,  by  the  exhibition  of  an  emetic.  According  to  Dr. 
Peschier,  the  white  of  one  egg  is  required  to  neutralize  four  grains 
of  the  poison.  Dr.  Taddei  strongly  advised  as  an  antidote  the  use 
of  wheat  flour,  or  gluten.  This  remedy  has  been  successfully  ad- 
ministered to  animals,  and  has  been  resorted  to  with  apparent  success 
in  the  human  subject.  The  free  exhibition  of  milk  has  been  highly 
recommended. 

Dr.  Buckler,  of  Baltimore,  in  1842,  proposed  the  use  of  a  mixture 
of  gold-dust  and  iron-filings,  and  adduced  some  experiments  on 
animals  in  support  of  its  efficacy ;  but  these  results  were  not  con- 
firmed by  the  experiments  of  Orfila.  {Toxicologie,  i.  687.)  More 
recently.  Dr.  C.  Johnston,  of  Baltimore,  exhibited  this  mixture  to  a 
gentleman  who  had  swallowed  eighty  grains  of  corrosive  sublimate, 
and  the  patient  recovered.  {Amer.  Jour.  Med.  Sci.,  April,  1863, 
340.)  Since,  however,  in  this  case,  previous  to  the  administration  of 
the  gold  mixture,  which  was  not  exhibited  until  about  twenty-five 


POST-MORTEM   APPEARANCES.  337 

inimitt's  alUT  the  itoison  Iiad  been  taken,  there  had  been  violent  and 
almost  incessant  vomiting  for  about  fifteen  minutes,  and  a  mixture 
of  white  of  egg  and  milk  had  been  freely  given,  it  is  by  no  means 
certain  that  the  alleged  antidote  had  any  part  whatever  in  the  recovery 
of  the  patient. 

Among  the  other  antidotes  that  have  been  advised  for  this  poison 
may  be  mentioned  stannous  chloride  (protochloride  of  tin),  iron  filings 
either  alone  or  mixed  witii  zinc,  the  hydrated  sulphides  of  iron, 
the  alkaline  carbonates,  and  meconic  acid  and  its  soluble  salts. 
Neither  of  these  substances,  however,  possesses  any  advantage  over 
tliose  mentioned  above,  and  in  fact  some  of  them  seem  to  be  entirely 
inert ;  moreover,  neither  of  them  is  as  likely  to  be  at  hand  as  either 
white  of  egg,  flour,  or  milk. 

Post-mortem  Appearances.— The  lining  membrane  of  the 
mouth,  fauces,  and  oesophagus  is  frequently  more  or  less  inflamed 
and  softened ;  but  cases  are  reported  in  which  these  parts  were  found 
in  a  perfectly  normal  condition.  The  action  of  this  poison  upon 
the  stomach  and  bowels  is  generally  much  greater  than  that  usually 
caused  by  arsenic.  The  coats  of  the  stomach  are  often  more  or  less 
corroded  and  softened ;  and  its  internal  surface  has  presented  a  dark, 
ulcerated  appearance.  In  a  case  cited  by  Dr.  Christison,  in  which 
the  patient  survived  thirty-one  hours,  the  coats  of  the  stomach  were 
perforated.  The  intestines,  especially  the  colon  and  rectum,  often 
present  signs  of  violent  inflammatory  action.  This  condition  has 
been  observed  in  cases  in  which  the  stomach  was  found  but  little 
affected.  The  urinary  organs  also  are  often  much  inflamed,  and  the 
bladder  greatly  contracted  and  nearly  or  altogether  empty.  An  in- 
stance is  related  in  which  the  bladder  was  reduced  to  the  size  of 
a  walnut ;  and  another,  that  of  a  child,  in  which  this  organ  was  no 
larger  than  a  marble. 

In  the  two  cases  of  the  three  children  already  mentioned,  which 
proved  fatal  in  three  and  eleven  hours  respectively,  the  mucous 
membrane  of  the  mouth,  pharynx,  and  oesophagus  was  found,  in 
several  places,  softened,  white,  and  could  be  easily  detached  by  the 
handle  of  the  scalpel.  The  mucous  surface  of  the  stomach'  and 
bowels  exhibited  patches  of  acute  inflammation,  and  here  and  there 
of  partial  erosion ;  at  these  places  its  color  was  of  a  deep  brown,  or 
of  an  eschar-like  hue.  On  the  inner  surface  of  the  left  ventricle 
of  the  heart,  in  the  elder  child,  there  were  observed  two  patches  of 


338  MERCURY. 

distinct  ecchymosis,  caused  by  the  effusion  of  blood  between  the 
investing  serous  membrane  and  the  muscular  tissue.  In  the  younger 
child,  also,  a  similar  appearance,  but  less  distinctly  marked,  was 
found.  No  other  appearances  are  mentioned  in  the  description  of 
these  cases. 

In  a  case  related  by  Dr.  H.  Williams  {Am.  Jour.  Med.  Sei.,  Jan. 
1851,  79),  in  which  thirty  grains  of  the  poison  proved  fatal  to  an 
adult  on  the  third  day,  the  following  appearances  were  observed 
twenty-five  hours  after  death.  The  stomach  was  contracted  for  the 
extent  of  about  two  inches,  at  its  middle  portion,  into  the  form  of 
a  dumb-bell.  It  contained  a  small  quantity  of  bright  yellow  fluid 
having  the  consistency  of  thin  gruel.  Its  larger  and  smaller  curva- 
tures presented  patches  of  dotted  injection,  of  a  bright  crimson  tint; 
and  the  mucous  membrane  was  a  little  softened  in  the  neighborhood 
of  the  most  vivid  red  patches.  Patches  of  beautifully  arborescent 
vascularity  were  also  observed  at  intervals  along  the  whole  extent  of 
the  small  intestines ;  the  large  intestines  were  healthy.  The  bladder 
was  contracted,  and  contained  about  a  drachm  of  turbid  urine. 
The  other  organs  of  the  body  were  healthy. 

In  the  case  reported  by  Dr.  Ogle,  fatal  in  sixty  hours,  the  lungs 
were  emphysematous,  and  all  the  cavities  of  the  heart  contained 
large  blood-coagula.  The  upper  part  of  the  oesophagus  was  natural, 
but  the  lower  part  was  of  a  rusty  color,  and  nearer  to  the  stomach 
it  was  corroded.  The  mucous  membrane  of  the  great  curvature  of 
the  stomach  presented  many  dark  lines,  showing  the  charring  effect 
of  the  poison  on  the  prominent  folds.  The  upper  portion  of  the 
duodenum  was  of  a  rusty  color,  and  beyond  this  it  was  soft  and 
swollen.  Below  this  point  the  small  intestine  was  covered  through- 
out with  an  adherent  fine,  white,  powdery  deposit.  The  brain  was 
watery,  and  the  subarachnoid  spaces  contained  more  than  usual  fluid. 

In  Dr.  Post's  case,  fatal  on  the  sixth  day,  twenty-seven  hours 
after  death,  there  being  no  signs  of  decomposition,  there  was  found 
marked  congestion  of  the  lungs,  and  the  heart  was  relaxed  and 
flabby ;  the  oesophagus  and  cardiac  extremity  of  the  stomach  were 
very  much  congested,  but  there  were  no  signs  of  ulceration.  The 
alimentary  tract  appeared  more  or  less  congested,  especially  the 
small  intestines.  The  kidneys  were  much  increased  in  size,  and 
were  heavier  than  normal ;  the  bladder  was  empty.  The  post-mortem 
plainly  indicated  ursemia,  produced  by  congestion  of  the  kidneys. 


chemical  properties.  339 

Chemical  Properties. 

General  Chemical  Nature. — Corrosive  sublimate  crystal- 
lizes, without  water  of  crystallization,  in  the  form  of  colorless, 
transparent,  rhombic  prisms.  Its  specific  gravity  has  been  variously 
stated  at  from  5.2  to  6.5.  It  has  an  exceedingly  styptic,  nauseous, 
metallic,  and  persistent  taste.  When  heated  to  a  temperature  of 
265°  C.  (509°  F.),  it  fuses  to  a  colorless  liquid,  which  boils  at  about 
295°  C.  (563°  F.),  evolving  an  extremely  acrid  and  poisonous  vapor. 
If  the  vapor  be  received  upon  a  cold  surface,  it  frequently  condenses 
in  the  form  of  white  crystalline  needles. 

Corrosive  sublimate  is  readily  decomposed  by  the  fixed  alkalies, 
forming  a  chloride  of  the  alkali  and  oxide  of  mercurv.  Cold  sul- 
phuric acid  fails  to  decompose  or  dissolve  it,  but  it  is  somewhat 
soluble,  without  decomposition,  in  nitric  and  hydrochloric  acids. 
When  in  aqueous  solution,  it  is  readily  decomposed  and  precipitated 
by  various  vegetable  and  animal  principles,  such  as  albumen,  fibrin, 
casein,  gluten,  and  tannic  acid.  Hence  the  utility  of  these  substances, 
as  antidotes,  in  poisoning  by  this  salt. 

Solubility.  1.  In  Water. — The  solubility  of  corrosive  sublimate 
in  water,  at  the  ordinary  temperature,  has  been  variously  stated  at 
from  nine  to  twenty  parts  of  the  fluid.  According  to  our  own  ex- 
periments, when  the  pure,  powdered  crystallized  salt  is  digested  with 
ten  times  its  weight  of  pure  distilled  water  at  a  temperature  of  about 
15.5°  C.  (60°  F.),  with  occasional  agitation,  for  twenty-four  hours, 
the  solution  then  filtered,  and  the  filtrate  cautiously  evajjorated  to 
dryness,  it  leaves  a  residue  indicating  that  one  part  of  the  salt  had 
dissolved  in  13.30  times  its  weight  of  the  liquid. 

According  to  most  observers,  the  salt  is  soluble  in  less  than  three 
times  its  weight  of  boiling  w^ater.  From  these  statements  it  is 
obvious  that  the  quantity  of  the  poison  that  may  be  taken  up  in 
solution  by  water  will  in  a  great  measure  depend  upon  the  tempera- 
ture of  the  latter. 

2.  In  Alcohol. — When  the  powdered  salt  is  agitated  for  some 
minutes,  at  the  ordinary  temperature,  with  two  parts  of  alcohol  of 
specific  gravity  0.800  (=  98  per  cent.),  the  solution  filtered,  and 
evaporated  to  dryness,  the  residue  indicates  that  one  part  of  the 
poison  had  dissolved  in  2.47  parts  of  the  liquid. 

On  digesting  the  powdered  salt  with  five  parts  of  common  whiskey 


340  MERCURY, 

for  twenty-four  hours,  at  the  ordinary  temperature,  with  frequent 
agitation,  one  part  of  the  former  required  fifteen  parts  of  the  latter 
for  solution. 

3.  In  Absolute  Ether. — When  powdered  corrosive  sublimate  is 
digested,  with  frequent  agitation,  for  twenty-four  hours,  with  five 
parts  of  absolute  ether,  at  a  temperature  of  about  15.5°  C  (60° 
F.),  one  part  of  the  salt  dissolves  in  8.8  parts  of  the  menstruum. 
The  salt  is  much  more  freely  soluble  in  ordinary  commercial  ether, 
this  liquid  usually  taking  up  about  one-third  of  its  weight  of  the 
poison. 

By  taking  advantage  of  the  solubility  of  corrosive  sublimate 
in  ether,  the  salt  may  be  separated  from  its  aqueous  solution,  or 
from  organic  mixtures.  If  one  grain  of  the  mercury  compound  be 
dissolved  in  one  hundred  grains  of  pure  water,  and  the  solution 
agitated  for  several  minutes  with  an  equal  volume  of  commercial 
ether,  the  latter  withdraws  from  the  water  0.67  of  a  grain  of  the 
salt.  According  to  M.  Karls,  the  presence  of  camphor  very  much 
increases  the  solvent  power  of  both  ether  and  alcohol  for  corrosive 
sublimate. 

4.  In  Chloroform. — Corrosive  sublimate  is  only  very  sparingly 
soluble  in  chloroform.  When  the  powdered  salt  is  occasionally  agi- 
tated during  twenty-four  hours  with  twenty  parts  of  this  liquid, 
at  the  ordinary  temperature,  one  part  of  the  salt  requires  seventeen 
hundred  parts  of  the  fluid  for  solution. 

Of  Solid  Corrosive  Sublimate. 

In  its  solid  state,  corrosive  sublimate  may  be  identified  by  a 
variety  of  reactions. 

1.  When  a  small  portion  of  the  salt  is  moistened  with  a  drop  of 
a  solution  of  potassium  iodide,  it  assumes  a  bright  scarlet  color, 
due  to  the  formation  of  mercuric  iodide,  which  is  soluble  to  a  color- 
less solution  in  excess  of  the  potassium  compound.  This  reaction  is 
extremely  delicate,  and  peculiar  to  the  mercuric  combinations.  The 
residue  obtained  from  the  evaporation  of  one  grain  of  water  con- 
taining the  1-1 000th  of  a  grain  of  corrosive  sublimate,  when  moist- 
ened with  the  reagent,  acquires  a  fine  scarlet  color ;  the  residue  from 
the  l-10,000th  of  a  grain  assumes  a  distinct  yellow  hue,  and  soon 
dissolves. 

2.  If  a  drop  of  a  strong  solution  of  potassium  iodide  be  placed 


TIEACTIONS   OF   CORROSIVE  SUBLIMATE.  3ll 

on  a  piece  ol'  bright  copper,  aiul  a  siiuill  <iuaiitity  of  corrosive  sul)- 
11  mate  atkled,  the  hitter  undergoes  decomposition,  and  the  copper 
becomes  stained  with  a  deposit  of  metallic  mercury,  vvhicli  when 
rubbed  with  a  soft  substance,  as  the  end  of  the  finger,  assumes  a 
bright  silvery  apppearance.  This  reaction  will  manifest  itself  with 
the  least  visible  quantity  of  the  mercurial  compound.  The  dried 
stain  is  readily  dissipated  by  heat.  If  in  this  experiment  the  potas- 
siuiu  iodide  solution  be  substituted  by  a  drop  of  hydrochloric  acid, 
the  same  metallic  deposit  takes  place,  and  the  reaction  is  equally 
delicate. 

3.  When  corrosive  sublimate  is  moistened  with  a  few  drops  of 
a  solution  of  stannous  chloride,  it  slowly  assumes  a  gray  color,  and 
finally  becomes  nearly  black,  from  the  separation  of  metallic  mer- 
cury. In  this  reaction  the  mercurial  compound  yields  up  the  whole 
of  its  chlorine  to  the  tin,  converting  the  latter  into  tetrachloride  of 
tin. 

4.  If  the  salt  be  treated  with  a  few  drops  of  a  solution  of  am- 
monium sulphide,  it  quickly  acquires  a  yellow  color,  which  in  a  little 
time  changes  to  black,  due  to  the  formation  of  sulphide  of  mercury. 
This  transition  of  color  is  peculiar  to  mercuric  combinations  of  the 
metal. 

5.  When  touched  with  a  strong  solution  of  caustie  potash  or  of 
soda,  it  immediately  assumes  a  yellow  or  brownish-yellow  color,  due 
to  the  production  of  mercuric  iodide.  This  reaction  serves  to  dis- 
tinguish corrosive  sublimate  from  calomel,  which  is  blackened  by 
the  reagent,  due  to  the  formation  of  mercurous  oxide.  Calomel  is 
also  blackened  by  caustic  ammonia,  whereas  the  color  of  corrosive 
sublimate  remains  unchanged. 

6.  When  a  small  quantity  of  corrosive  sublimate  is  heated  in  a 
reduction-tube,  it  volatilizes  unchanged,  and  recondenses  in  the  cooler 
portion  of  the  tube,  usually  in  the  form  of  groups  of  crystals  of  the 
forms  illustrated  in  Plate  V.,  fig.  2.  The  exact  forms  of  these  crys- 
tals, however,  will  depend  in  great  measure  upon  the  quantity  of 
the  salt  employed  :  the  most  perfect  crystals  are  obtained  by  using 
only  a  very  minute  portion  of  the  salt;  when  a  comparatively  large 
quantity  is  employed,  the  sublimate  is  in  the  form  of  a  dense  crys- 
talline mass,  destitute  of  any  distinct  crystals. 

In  applying  this  test,  the  analyst  should  bear  in  mind  that  am- 
monium salts,  oxalic  acid,  and  arsenious  oxide  will  also,  like  corro- 


342  MERCURY. 

sive  sublimate  and  certain  other  compounds  of  mercury,  completely 
volatilize,  with  the  production  of  a  white  sublimate.  The  sublimate 
from  arsenious  oxide,  however,  is  in  the  form  of  octahedral  crystals, 
whereas  that  from  corrosive  sublimate  is  never  in  the  octahedral 
form ;  moreover,  the  former  substance  does  not  fuse  before  volatil- 
izing. The  sublimates  from  oxalic  acid  and  ammonium  salts  may 
closely  resemble  that  from  the  mercurial  compound,  but  the  latter  is 
readily  distinguished  from  these,  as  well  as  from  all  other  volatile 
white  powders,  in  that  when  touched  with  a  solution  of  potassium 
iodide  it  assumes  a  bright  scarlet  color. 

7.  When  a  small  quantity  of  perfectly  dry  corrosive  sublimate 
is  intimately  mixed  with  several  times  its  volume  of  recently  ignited 
sodium  carbonate,  and  the  mixture  heated  in  a  reduction-tube,  the 
heat  being  very  gradually  increased,  it  yields  a  globular  sublimate  of 
metallic  mercury ;  at  the  same  time  an  equivalent  quantity  of  sodium 
chloride  is  formed  and  remains  in  the  residue.  The  reaction  in  this 
case  is  expressed  as  follows:  HgCl2  +  Na2C03=2NaCl  +  Hg  + 
COg  +  O.  This  reaction  will  manifest  itself  with  the  least  visible 
quantity  of  the  corrosive  salt,  at  least  if  the  operation  be  conducted 
in  a  very  narrow  or  contracted  tube ;  it  must  be  remembered,  how- 
ever, that  the  production  of  the  metallic  sublimate  is  common  to  all 
the  compounds  of  mercury. 

When  the  sublimate  thus  obtained  is  examined  under  a  low 
power  of  the  microscope,  it  will  be  found  to  consist  of  minute,  opaque, 
spherical  globules,  which  under  incident  light  have  an  exceedingly 
brilliant,  metallic  lustre.  These  characters  readily  distinguish  the 
mercurial  from  all  other  sublimates.  The  presence  of  the  chlorine 
in  the  sodium  chloride,  resulting  from  the  decomposition  of  the  cor- 
rosive sublimate,  may  be  shown  by  dissolving  the  saline  residue  in 
a  little  warm  water,  acidulating  the  solution  with  nitric  acid,  and 
then  adding  a  little  silver  nitrate,  when  the  chlorine  will  be  thrown 
down  as  white  chloride  of  silver,  which  is  insoluble  in  nitric  acid 
but  readily  soluble  in  ammonia.  Similar  results  would  be  obtained 
if  the  substance  submitted  to  examination  was  calomel ;  but  the 
insolubility  of  the  latter  in  water  readily  distinguishes  it  from  cor- 
rosive sublimate.  Before  resorting  to  this  method  of  reduction  in 
the  examination  of  a  suspected  substance,  the  operator  should  satisfy 
himself  that  the  sodium  carbonate  about  to  be  employed  is  perfectly 
free  from  chlorine. 


AMMONIA    TEST. 


343 


Of  Sot.utions  of  Corrosivb  Sublimate. 

Pure  aquoous  solutions  of  corrosive  sublimate  are  colorless,  and, 
whei)  not  very  dilute,  feebly  redden  litmus-paper.  The  nauseous 
metallic  taste  of  the  salt  is  well  marked,  even  in  very  highly  diluted 
solutions.  On  cooling-,  hot  concentrated  solutions  throw  down  the 
excess  of  the  salt  in  its  crystalline  state.  When  a  drop  of  a  tolerably 
stronir  solution  is  allowed  to  evaporate  spontaneously,  the  residue 
usually  consists  of  long,  transparent,  crystalline  needles  and  prisms; 
but  from  more  dilute  solutions  it  is  generally  in  the  form  of  a  con- 
fused crystalline  film.  The  crystallization  of  the  salt  is  readily  in- 
terfered with  by  the  presence  of  organic  matter. 

In  the  following  investigations  in  regard  to  the  chemical  behavior 

of  solutions  of  corrosive  sublimate,  pure  aqueous  solutions  of  the 

salt  were  employed.     The  fractions  indicate  the  fractional  part  of  a 

grain  of  the  anhydrous  salt  present  in  one  graiu  of  the  liquid ;  and 

the  results,  unless  otherwise  stated,  refer  to  the  behavior  of  one  grain 

of  the  solution. 

1.  Ammonia. 

Aqua  amraoniEe  produces  in  solutions  of  corrosive  sublimate  a 
white,  flocculent  precipitate  known  as  mercurammonium  chloride, 
HgNH^Cl;  thus:  HgCl^  +  2NH„H0  =  HgNH.Cl  +  NH„C1 -j- 
2H2O.  The  precipitate  is  soluble  in  large  excess  of  the  precipitant, 
and  readily  soluble  in  the  mineral  acids;  it  is  also  soluble  in  some  of 
the  salts  of  ammonium,  but  insoluble  in  ammonium  chloride. 

1.  _i^  grain  of  corrosive  sublimate,  in  one  grain  of  water,  yields 

with  the  reagent  a  very  abundant  precipitate.  If  the  mercu- 
rial solution  be  exposed  to  the  vapor  of  ammonia,  it  yields  the 
same  reaction. 

2.  YoW  grain  yields  a  quite  good  deposit. 

3.  .^1^^  grain  :  a  quite  satisfactory  reaction  by  either  ammonia  or 

its  vapor. 

4.  y^^iy^j-^  grain  :  a  quite  perceptible  turbidity. 

This  reagent  also  produces  white  precipitates  in  solutions  of 
various  other  substances  besides  mercuric  combinations.  But  if  the 
mercurial  precipitate  be  dried  and  heated,  it  readily  volatilizes  with- 
out residue,  in  which  respect  it  differs  from  all  other  metallic  pre- 
cipitates produced  by  the  reagent.  When  heated  with  a  solution  of 
potassium  hydrate,  the  precipitate  is  decomposed,  with  the  production 


344  MERCUEY. 

of  yellow  oxide  of  mercury.     The  precipitate  is  also  decomposed  by 
stannous  chloride,  with  the  separation  of  metallic  mercury. 

2.  Potassium  and  Sodium  Hydrates. 

The  fixed  caustic  alkalies,  when  added  in  not  sufficient  quantity 
to  effect  complete  decomposition,  throw  down  from  quite  strong  solu- 
tions of  corrosive  sublimate  reddish-brown  amorphous  precipitates 
consisting  of  a  compound  of  mercuric  oxide  and  the  undecomposed 
chloride  of  the  metal ;  but  when  the  reagent  is  added  in  excess  the 
precipitate  has  a  yellow  color,  and  consists  alone  of  mercuric  oxide, 
HgO.  The  precipitate  is  insoluble  in  excess  of  the  precipitant,  but 
readily  soluble  in  free  acids. 

1.  y^  grain  of  corrosive  sublimate  yields  a  rather  copious,  reddish- 

brown  or  yellow  deposit. 

2.  -5^  grain  yields  only  a  slight  cloudiness. 

The  production  of  a  reddish-brown  precipitate,  which  becomes 
yellow  upon  the  further  addition  of  the  alkaline  reagent,  is  peculiar 
to  mercuric  combinations.  The  only  other  metals  that  yield  yellow 
precipitates  with  the  reagent  are  the  rare  substances  platinum  and 
uranium  :  the  precipitate  from  the  former  of  these  is  usually  in  the 
form  of  octahedral  crystals ;  but  the  precipitate  from  the  latter,  like 
that  from  mercurial  compounds,  is  amorphous  and  insoluble  in  excess 
of  the  precipitant. 

When  the  precipitated  mercuric  oxide  is  collected,  dried,  and 
strongly  heated  in  a  reduction-tube,  it  undergoes  decomposition,  with 
the  evolution  of  free  oxygen  gas  and  the  production  of  a  globu- 
lar sublimate  of  metallic  mercury.  This  reaction  will  serve  for  the 
identification  of  the  merest  trace  of  the  mercurial  precipitate.  The 
presence  of  the  chlorine  of  the  corrosive  sublimate  in  the  liquid  from 
which  the  mercury  was  precipitated  may  be  shown  by  acidulating 
the  solution  with  nitric  acid,  and  then  adding  silver  nitrate,  when  it 
will  yield  a  white  precipitate  of  silver  chloride. 

The  normal  carbonates  of  the  fixed  alkalies,  when  added  in  limited 
quantity,  throw  down  from  one  grain  of  a  1-1 00th  solution  of  cor- 
rosive sublimate  a  quite  good  yellowish  precipitate ;  when  an  excess 
of  the  reagent  is  employed,  the  precipitate  has  a  brick-red  color. 
A  similar  quantity  of  a  l-500th  solution  of  the  salt  yields  only  a 
slight  turbidity. 


SULPIIURFyrTED    HYDROGKN     TEST.  345 


3.  Potassium  Iodide. 

Tills  reiio;ent  produces  in  solutions  of  corrosive  sublimate  a  brij^ht 
scarlet  amorphous  precipitate  of  mercuric  iodide,  Hglg,  which  is 
readilv  soluble  in  excess  of  the  precipitant,  as  well  as  in  large  excess 
of  the  mercurial  solution.  At  first  the  precipitate  has  frequently  a 
yellow  color,  but  it  quickly  becomes  scarlet,  except  if  only  in  minute 
quantitv,  when  the  yellow  color  may  be  permanent.  The  iodide  of 
mercury  is  also  soluble  in  the  alkaline  chlorides  and  in  alcohol,  but 
onlv  slowly  soluble  in  the  diluted  mineral  acids;  strong  nitric  and 
sulphuric  acids  readily  decompose  it,  with  the  elimination  of  iodine. 

1.  _L_  grain  of  the  salt  yields  a  copious,  scarlet  precipitate. 

2.  YjjViT  grain  :  a  reddish-yellow  deposit. 

3.  -s-sinj"  grain  yields,  with  a  very  minute  quantity  of  the  reagent,  a 

quite  satisfactory  yellow  precipitate. 
The  production  of  a  scarlet  precipitate  by  this  reagent  is  peculiar 
to  solutions  of  mercuric  salts.  The  iodide  of  mercury,  when  washed, 
dried,  and  heated  in  a  reduction-tube,  volatilizes  unchanged,  and  re- 
condenses  in  the  form  of  a  yellow,  partly  crystalline  sublimate,  the 
color  of  which  slowly  changes  to  scarlet.  When  the  dried  precipi- 
tate is  intimately  mixed  with  recently  ignited  sodium  carbonate  and 
heated  in  a  reduction-tube,  it  yields  a  sublimate  of  metallic  mercury. 

4.  Sulphuretted  Hydrogen. 

When  somewhat  concentrated  neutral  or  acidulated  solutions  of 
corrosive  sublimate  are  treated  with  a  relatively  small  quantity  of 
sulphuretted  hydrogen  gas  or  of  ammonium  sulphide,  they  yield  a 
precipitate  which,  at  least  when  the  mixture  is  agitated,  has  a  pure 
white  color,  and  consists  of  mercuric  sulphide  and  undecomposed 
corrosive  sublimate.  On  the  further  addition  of  the  reagent,  the 
precipitate  acquires  a  yellow,  then  a  brown  color,  and  finally  be- 
comes blaclc,  when  it  consists  alone  of  the  sulphide  of  mercury. 
From  more  dilute  solutions  the  precipitate  has  at  first  a  brownish 
color. 

The  precipitated  mercuric  sulphide  is  insoluble  in  nitric  and 
hydrochloric  acids,  even  on  the  application  of  heat;  but  it  is  readily 
decomposed  and  dissolved  by  cold  nitro-hydrochloric  acid,  with  the 
separation  of  free  sulphur  and  the  formation  of  mercuric  chloride 


346  MERCURY. 

and  more  or  less  mercuric  sulphate,  the  latter  compound  being  derived 
from  the  oxidation  of  some  of  the  sulphur.  It  is  insoluble  in  the 
caustic  alkalies,  and  in  the  alkaline  sulphides. 

The  following  results  in  regard  to  the  reactions  of  this  test  refer 
to  the  behavior  of  ten  grains  of  the  corrosive  sublimate  solution 
when  acidulated  with  hydrochloric  acid  and  subjected  to  the  action 
of  a  slow  stream  of  the  washed  sulphuretted  gas. 

1.  1-lOOth  solution  (=^  grain   of  HgClg)  yields  an  immediate 

brownish  precipitate,  which  soon  assumes  a  dark  brown  color, 
and  ultimately  becomes  black,  the  final  precipitate  being  quite 
copious. 

2.  1-lOOOth  solution  yields  a  yellowish-brown,  brown,  then  a  rather 

copious  black  precipitate. 

3.  1— 10,000tli  solution  :  the  liquid  immediately  assumes  a  brownish 

color,  then  small  brownish  flakes  separate,  and  after  a  little  time 
there  is  a  good  brownish  deposit. 

4.  1 -25,000th  solution:    almost  immediately  the  liquid  assumes  a 

yellowish  color,  and  in  a  few  minutes  very  small  brownish 
flakes  appear,  which  after  some  time  subside  to  a  very  distinct 
deposit. 

5.  l-50,000th  solution  :  very  soon  the  fluid  becomes  turbid,  and  after 

standing  some  time  throws  down  a  just  perceptible  yellowish 
precipitate. 

6.  1-1 00,000th  solution,  when  saturated  with  the  gas  and  allowed  to 

stand  several  hours,  undergoes  no  well-marked  change. 

The  progressive  change  of  color  from  white  to  black,  of  the  pre- 
cipitate produced  by  this  reagent,  is  peculiar  to  solutions  of  mercuric 
salts.  But  this  change,  as  shown  above,  is  well  marked  only  in  com- 
paratively strong  solutions  of  the  mercurial  salt;  and  the  production 
of  a  black  or  brownish  precipitate  is  not  in  itself  characteristic  of 
mercury,  since  there  are  several  other  metals  that  yield  similar  re- 
sults, even  from  acidulated  solutions. 

Mercuric  sulphide  differs  from  all  other  black  precipitates,  pro- 
duced under  like  conditions,  in  that  when  thoroughly  dried,  and 
heated  in  a  reduction-tube,  it  completely  volatilizes,  without  residue 
or  decomposition,  and  yields  a  black  sublimate  having  a  metallic 
appearance.  Again,  when  mixed  with  anhydrous  sodium  carbonate, 
and  heated  in  a  reduction-tube,  it  undergoes  decomposition,  with  the 
production  of  a  globular  sublimate  of  metallic  mercury.     Either  of 


STANNOUS   CHLORIDE   TEST.  347 

these  mctliods  (hut  the  latter  is  preferahle)  will  serve  for  the  identi- 
fication of  very  inimito  traces  of  the  mercurial  conipoiinfl. 

It"  the  liquid  Irotn  which  the  mercury  was  precipitated  by  the 
sulphur  reagent  was  not  acidulated  with  hydrochloric  acid  previous 
to  the  application  of  the  reagent,  it  will  serve  for  the  detection  of 
the  chlorine  of  the  corrosive  sublimate,  which  element  now  exists  as 
free  hydrochloric  acid.  For  this  purpose  the  filtered  liquid  is  gently 
heated  until  the  odor  of  the  sulphuretted  hydrogen  has  entirely 
disappeared,  and  then  treated  with  a  solution  of  silver  nitrate. 

5.  Stannoiis  Chloride. 

When  a  limited  quantity  of  stannous  chloride  is  added  to  solutions 
of  corrosive  sublimate,  the  latter,  giving  up  a  portion  of  its  chlorine 
to  the  tin,  is  reduced  to  mercurious  chloride,  or  calomel,  which  falls 
as  a  white  precipitate,  the  reaction  being  2HgC]2  +  SnCl2  =  SnCl4  + 
HgjClg.  In  the  presence  of  an  excess  of  the  reagent  the  mercury  is 
entirely  deprived  of  its  chlorine,  and  separates  as  a  dark  gray  pre- 
cipitate of  exceedingly  minute  globules  of  the  metal.  The  reaction 
in  this  case  is  HgCl2  +  SnCl2  =  SnCl4  +  Hg.  The  separation  and 
subsidence  of  the  metallic  precipitate  are  much  facilitated  by  heating 
the  mixture  with  a  little  hydrochloric  acid;  if  the  clear  supernatant 
liquid  be  then  decanted,  and  the  residue  again  heated  with  a  little 
fresh  hydrochloric  acid,  the  finely  divided  mercury  will  unite  into 
larger  globules.  The  hydrochloric  acid  employed  in  this  operation 
should  be  perfectly  free  from  nitric  acid,  otherwise  the  metallic 
globules  may  disappear,  being  dissolved.  This  test  may  be  con- 
veniently applied  in  a  watch-glass. 

1.  YQ-g-  grain  of  corrosive  sublimate,  in  one  grain  of  water,  yields 

with  the  reagent  a  rather  copious  precipitate,  which  at  first  is 
white,  but  quickly  changes  to  a  gray  color,  and  then  becomes 
almost  black. 

2.  YWUT  gi'ain  yields  much  the  same  results  as  1. 

3.  -g-oVo"  gi'aiu  :  a  quite  good  precipitate. 

4.  Yo,VoT7  grain  yields  a  quite  distinct  reaction. 

The  production  of  metallic  globules  by  this  test  is,  of  course, 
peculiar  to  solutions  of  mercury.  When  the  precipitate  is  present 
in  only  minute  quantity,  its  globular  nature  may  still  be  readily 
recognized  by  means  of  a  hand-lens  or  a  low  power  of  the  micro- 
scope.     If  the  precipitate  be  stirred  with  a  small  piece  of  bright 


348  MERCUKY. 

copper-foil,  the  latter  receives  a  coating  of  metallic  mercury,  which 
when  rubbed  by  a  soft  body  assumes  a  bright  silvery  appearance. 
In  this  manner,  especially  by  the  aid  of  a  drop  of  hydrochloric  acid 
and  a  gentle  heat,  the  true  nature  of  a  mercurial  deposit  that  will 
not  furnish  satisfactory  globules  may  sometimes  be  readily  deter- 
mined. 

It  is  important  to  bear  in  mind,  in  the  application  of  this  test, 
that  the  reaction  of  stannous  chloride  is  interfered  with  or  entirely 
prevented  by  the  presence  of  alkaline  chlorates,  and  also  of  free 

nitric  acid. 

6.   Copper  Test. 

When  a  small  slip  of  bright  copper-foil  is  placed  in  a  normal 
solution  of  corrosive  sublimate,  the  latter  is  decomposed,  with  the 
deposition  of  metallic  mercury  upon  the  copper.  The  delicacy  of 
this  reaction  is  much  increased  by  acidulating  the  solution  with  hy- 
drochloric acid,  and  also  by  heat.  The  deposited  mercury,  when 
separated  from  normal  solutions  of  the  salt,  has  usually  a  dark  gray 
color;  whilst  when  from  acidulated  solutions  it  has  generally  a 
bright  silvery  appearance  :  its  exact  appearance,  however,  will  depend 
much  upon  the  thickness  of  the  deposit,  which  in  its  turn  will,  of 
course,  depend  upon  the  strength  of  the  solution  and  the  size  of  the 
copper-foil  employed.  When  the  deposit  has  a  dull  color,  it  imme- 
diately acquires  a  bright,  mirror-like  appearance  on  being  rubbed 
with  a  piece  of  soft  wood  or  any  similar  substance. 

The  same  metallic  deposit  will,  of  course,  make  its  appearance 
when  a  drop  of  the  mercury  solution  is  placed  on  a  piece  of  bright 
copper  plate.  Under  these  circumstances,  it  has  been  proposed  to 
touch  the  copper,  through  the  mercurial  solution,  with  a  needle  of 
zinc.  This  somewhat  facilitates  the  decomposition  of  the  mercurial 
compound,  but  at  the  same  time  it  causes  the  separated  mercury  to 
be  distributed  over  a  greater  surface,  part  of  it  being  deposited  upon 
the  immersed  end  of  the  zinc. 

When  a  small  piece  of  the  coated  copper-foil  is  carefully  washed, 
dried  at  a  moderate  temperature,  in  a  water-bath,  and  heated  in  a 
narrow,  perfectly  dry  reduction-tube,  the  mercury  volatilizes,  and  re- 
condenses  in  the  cooler  portion  of  the  tube,  forming  a  mist-like  sub- 
limate. Under  a  low  power  of  the  microscope,  this  sublimate  will 
be  found  to  consist  of  innumerable  spherical  globules,  which  are 
opaque  to  transmitted  light  and  present  a  bright  silvery  appearance- 


COPPER   TEST, 


349 


when  viewed  undor  incident  lijjjlit.      These  characters  readily  di.s- 
tini^nish  tlie  niorcnrial  IVoin  nil  other  sublimates. 

In  the  following  investigations  in  regard  to  the  limit  of  this  test, 
one  gi-ain  of  the  mercurial  solution,  placed  in  a  thin  watch-glass,  was 
acidulated  with  hydrochloric  acid,  and  the  mixture  heated  with  a 
small  fragment  of  the  copper-foil. 

1.  ^^  grain  of  corrosive  sublimate  imparts  to  the  copper  an  im- 

mediate lustre,  and  very  soon  the  deposit  becomes  comparatively 
thick.  This  reaction  takes  place  about  equally  well  without  the 
presence  of  the  free  acid  or  the  aid  of  heat.  The  copper  em- 
ployed should  measure  about  4-  by  -^^  of  an  inch  in  extent. 
When  the  washed  and  dried  coated  copper  is  heated  in  a  narrow 
reduction-tube,  it  yields  a  very  good  globular  sublimate,  many 
of  the  globules  measuring  --^-^q  of  an  inch  in  diameter. 

2.  —^-^  grain :  when  the  copper  employed  measures  about  ^  by  ^V 

of  an  inch  in  extent,  it  immediately  assumes  a  silvery  appear- 
ance, and  in  a  little  time  receives  a  gray  coating.  Similar  re- 
sults are  obtained  without  the  aid  of  heat.  Without  either  the 
free  acid  or  heat,  the  deposit  begins  to  form  in  a  very  little  time ; 
by  heat  alone,  immediately.  The  coated  copper,  when  heated 
in  a  small  reduction-tube,  yields  a  very  satisfactory  globular 

sublimate. 

3.  i_^  grain :  when  the  acidulated  liquid  is  heated  with  a  slip 

of  copper  measuring  about  i^o  '^7  To  of  an  inch  in  extent,  the 
mercurial  deposit  manifests  itself  immediately,  and  very  soon 
becomes  satisfactory.  If  the  coated  copper  be  heated  in  a  very 
narrow  reduction-tube,  it  yields  a  sublimate  which  is  quite  per- 
ceptible to  the  naked  eye,  and  which,  under  the  microscope,  is 
found  to  consist  of  innumerable  spherical  globules. 

When  deposits  but  little  smaller  than  that  just  considered  are 
heated  in  a  reduction-tube  of  the  ordinary  form,  even  of  very  nar- 
row bore,  the  results  are  by  no  means  uniform.  Very  uniform  results, 
however,  may  be  obtained  in  the  following  manner.  A  quite  thin 
and  perfectly  clean  tube,  of  about  1-lOth  of  an  inch  in  diameter,  is 
drawn  out  into  a  small  capillary  neck,  as  shown  in  Fig.  11,  A.  The 
coated  copper  is  then  introduced,  through  the  wider  portion  of  the 
cooled  tube,  to  the  point  c,  the  neck  of  the  tube  moistened  with  water  or 
wrapped  with  wet  cotton,  and  the  wider  end  very  carefully  fused  shut 
by  a  small  blow-pipe  flame,  when  the  fusion  is  slowly  advanced  to 


350  MEECURY. 


the  copper,  as  illustrated  in  B.  The  capillary  end  of  the  tube  may 
now  be  fused  shut.     When  the  tube,  thus  prepared,  is  wiped  and 

examined  under  the  microscope, 
^^^-  ^^-  the  mercurial  sublimate  will  be 

found    at   about   the    point   m, 


forming  a  narrow  ring  of  well- 
:b  defined  globules.    This  method 

also  possesses  the  advantage  of 
„  ^^      ,.     .      ,  .T .    .  ■         allowing  the  higher  powers  of 

Tubes  for  sublimation  of  mercury.    Natural  size.  ^  . 

the  microscope  to  be  applied, 
since  these  tubes  may  readily  be  prepared  with  walls  not  exceeding 
l-200th  of  an  inch  in  thickness.  The  tube  containing  the  subli- 
mate may  be  reserved  for  future  reference  :  after  long  periods,  how- 
ever, the  sublimate  deteriorates  somewhat,  and  may  even,  if  only  in 
minute  quantity,  entirely  disappear. 

4.  YS.oTo"  grain  :  if  the  acidulated  solution  be  heated,  and  as  the 
liquid  evaporates  its  place  supplied  with  pure  water,  the  copper 
in  a  little  time  presents  a  silvery  appearance,  and  before  long 
acquires  a  very  decided  gray  coating.  When  the  coated  copper 
is  heated  in  a  tube  of  the  above  form,  it  yields  a  sublimate  which 
is  visible  to  the  unaided  eye,  and  which,  under  an  amplification 
of  about  seventy-five  diameters,  is  found  to  consist  of  a  ring  of 
well-defined  globules.  In  a  number  of  instances  over  one  hun- 
dred globules,  varying  in  size  from  1-lOOOth  to  l-10,000th  of 
an  inch  in  diameter,  were  counted  in  a  single  field  of  the  ob- 
jective ;  many  of  the  globules  measured  over  l-2333d  of  an 
inch  in  diameter. 
6.  -sTj-.VoT  grain :  when  the  slip  of  copper  employed  measures  only 
about  2V  ^y  4¥  of  ^^  ^^^^^  ^^  extent,  the  results  obtained  are 
very  similar  to  those  described  under  4. 
6.  _j_i_.g_g.  grain  :  the  copper,  after  continued  heating  and  renewal 
of  the  evaporated  liquid  by  water,  acquires  a  quite  distinct 
metallic  tarnish,  and  when  heated  in  a  tube  of  the  above  form, 
yields  a  very  satisfactory  globular  sublimate.  In  some  few  in- 
stances over  one  hundred  globules  were  obtained,  several  of 
which,  singly,  measured  over  l-1750th  of  an  inch  in  diameter; 
the  greater  number  of  the  globules,  however,  were  quite  small : 
none  less  than  the  l-10,000th  of  an  inch  in  diameter  were 
counted.    In  a  majority  of  the  experiments  made,  the  sublimate 


COPPER  TEST.  nf)! 

contained  about  fifty  well-defined  globules,  most  of  wliicii  were 
usually  in  a  sinijlo  field  of  a  two-lliirds  inoli  ol)jeot-«i;ljiss.     So 
far  as  the  evidence  of  the  presence  of  niercury  is  concerned,  this 
quantity  of  corrosive  sublimate,  when  manipulated  in  the  above 
manner,  will  yield  just  as  satisfactory  results  as  a  much  larger 
quantity,  the  only  difference  being  in  the  absolute  number  and 
size  of  the  globules  obtained. 
7.  zT^.Tiii)  grain :  the  copper,  even  after  prolonged  heating,  under- 
goes but  little  change  in  appearance.     But  when  washed,  dried, 
and  heated   in  a  tube,  as  many  as  twenty  satisfactory  mercurial 
globules  were  obtained,  the  largest  of  which   measured  about 
l-3000th   of  an   inch   in  diameter;    the  diameter  of   most  of 
them,  however,  varied  from  l-5000th  to  l-lU,000th  of  an  inch. 
Most  of  the  sublimates  obtained  contained  from  five  to  ten 
globules  measuring  or  exceeding  l-5000th  of  an  inch  in   di- 
ameter. 
For  the  identification  of  these  mercurial  globules  an  amplifica- 
tion of  about  seventy-five  diameters  is  generally  the  most  useful. 
Under  this  power  a  globule  measuring  l-3000th  of  an  inch  in 
diameter  is  very  readily  identified  :    such   a  globule,  if    a   perfect 
sphere,  would  weigh  only  about  the  1-1 5,000,000th  of  a  grain.     So, 
also,  under  this  power,  globules  of  the  l-5000th  of  an  inch  in  diam- 
eter are  very  distinct  and  quite  satisfactory:  a  globule  of  this  size 
would  weigh  about  l-70,000,000th  of  a  grain.     And  even  when  of 
l-7000th  of  an  inch,  their  spherical  nature  may  still  be  determined 
with  considerable  certainty :  such  a  globule  would  Aveigh  only  about 
1-1 90,000,000th  of  a  grain.     But  under  this  amplification  globules 
of  only  l-10,000th  of  an  inch  in  diameter  appear  as  mere  opaque 
points  under  transmitted  light.     Under  an   amplification  of  about 
two  hundred  and  fifty,  a  globule  of  l-10,000th  of  an  inch  in  diam- 
eter may  be  satisfactorily  determined ;  and  even  when  of  only  the 
l-15,000th  of  an  inch,  their  spherical  outline  may  still  be  recognized 
with  considerable  certainty. 

On  account  of  the  curvature  of  the  glass  tube,  a  one-fifth  inch 
objective,  or  an  amplification  of  about  two  hundred  and  fifty  diam- 
eters, is  about  the  highest  power  that  can  be  satisfactorily  employed 
for  these  identifications.  When  upon  a  flat  surface,  the  true  nature 
of  globules  much  smaller  than  any  of  those  mentioned  above  can 
be  readily  determined.     Thus,  with  a  one-eighth  inch  objective  a 


352  MERCURY. 

globule,  or  "artificial  star/'  measuring  only  the  l-25,000th  of  an 
inch  in  diameter,  and  weighing  about  l-9,000,000,000th  of  a  grain, 
will  present  the  characters  of  sphericity  and  opacitj'-,  and  reflect  in- 
cident light.  It  need  hardly  be  observed  that  it  is  not  intended  to 
imply  that  quantities  of  mercury  in  themselves  no  greater  than  these 
can  be  recovered  from  a  solution  and  reproduced  in  the  globular 
form.  From  the  above  experiments  it  would  appear  that  even 
under  the  most  favorable  conditions  the  least  quantity  of  corrosive 
sublimate  from  which  the  mercury  can  thus  be  reproduced  is  about 
the  l-100,000th,  or  at  least  l-500,000th,  of  a  grain. 

It  may  be  remarked  that  in  the  above  experiments  the  amount 
of  metallic  mercury  present  in  the  corrosive  sublimate  was  as  100  is 
to  135.5.  It  may  also  be  added  that  from  these  experiments  it 
would  appear  that  mercury  is  not  as  readily  volatilized  by  continued 
heating  with  boiling  water  as  is  usually  supposed.  This  view  is  also 
borne  out  by  the  experiments  of  Fresenius.     [Quantitative  Analysis.) 

The  test  now  under  consideration  has  an  advantage  over  ordinary 
liquid  tests,  in  that  it  is  not  as  readily  affected  by  dilution.  Thus, 
ten  grains  of  a  l-100,000th  solution  of  the  mercurial  compound 
will  yield  after  a  time,  even  upon  renewal  of  the  evaporated  liquid, 
very  nearly  as  good  results  as  one  grain  of  a  1-1 0,000th  solution. 
Beyond  a  certain  limit,  however,  this,  like  all  other  tests,  will  en- 
tirely fail  to  act.  Another  advantage  possessed  by  this  test  is  that 
while  being  applied  to  a  solution  the  latter  may  be  concentrated  to 
almost  any  extent. 

Fallacies. — The  mere  fact  of  a  metallic  deposit  being  formed 
upon  the  copper,  in  the  application  of  this  test,  is  not  in  itself  posi- 
tive evidence  of  the  presence  of  mercury,  especially  if  the  solution 
be  acidulated  and  heated,  since  arsenic,  antimony,  silver,  bismuth, 
platinum,  palladium,  and  some  few  other  metals  are  deposited  under 
similar  conditions.  Of  these  various  metals,  however,  the  only  ones 
that,  like  mercury,  have  a  white  silvery  appearance  are  silver  and 
bismuth.  Moreover,  the  only  ones  which,  like  that  metal,  will 
deposit  from  cold  solutions  are  silver,  platinum,  and  palladium. 
When,  therefore,  the  deposition  takes  place  from  a  cold  solution,  and 
has  a  bright  silvery  lustre,  or  acquires  it  by  friction,  the  deposit  is 
most  probably  mercury ;  but  it  might  be  silver. 

Of  the  various  metals  that  might  thus  be  deposited,  even  from 
heated  acidulated  solutions,  the  only  ones  that  will  volatilize  and 


SILVER   NITRATE  TEST.  363 

yield  a  siil)linui(e,  when  tlie  coated  ooj)|)er  i.s  lieated  in  a  reduction- 
tube,  are  mercury,  arsenic,  and  antimony.  But  the  spherical  nature, 
as  well  as  the  opacity,  of  the  globules  under  transmitted  light,  and 
their  bright  silvery  lustre  under  incident  light,  of  the  mercurial 
sublimate,  readily  distinguish  it  from  the  octahedral  crystalline  sub- 
limate protlucod  by  arsenic,  and  from  the  deposit  occasioned  by 
antimony. 

Metallic  zinc,  bismuth,  cadmium,  tin,  silver,  nickel,  iron,  lead, 
arsenic,  and  antimony  will  also,  like  copper,  decompose  solutions  of 
corrosive  sublimate,  with  the  formation  of  a  coating  of  metallic  mer- 
cury upon  the  applied  metal.  But  neither  of  these  metals  has  for 
this  purpose  any  advantage  over  metallic  copper,  and  in  most  in- 
stances the  reaction  is  very  much  less  delicate  than  when  that  metal 
is  employed. 

So,  also,  if  the  acidulated  mercurial  solution  be  placed  in  a  small 
platinum  or  gold  dish  and  the  metal  touched,  through  the  solution, 
with  a  thin  wire  of  zinc,  iron,  tin,  or  any  other  of  the  above-named 
metals,  the  salt  undergoes  decomposition  by  galvanic  action,  the 
mercury  being  deposited  chiefly  upon  the  platinum  or  gold,  but  partly 
upon  the  other  metal.  Similar  results  may  be  obtained  by  applying 
a  small  slip  of  gold  or  platinum-foil  to  a  corresponding  slip  of  tin, 
zinc,  or  iron,  or  to  a  small  cylinder  of  either  of  these  metals,  and 
immersing  the  combination  in  the  acidulated  mercurial  solution. 
Some  of  these  galvanic  combinations  are  extremely  delicate  in  their 
reactions ;  but  they  are  not  as  well  adapted  for  the  detection  of  very 
minute  quantities  of  mercury  as  the  method  by  copper  alone,  as 
before  described. 

7.  Silv&r  Nitrate. 

This  reagent  decomposes  neutral  and  acidulated  solutions  of  cor- 
rosive sublimate,  with  the  production  of  a  white,  amorphous  pre- 
cipitate of  silver  chloride,  AgCl,  which  is  insoluble  in  nitric  acid. 
In  its  pure  state  silver  chloride  is  very  readily  soluble  in  ammonia, 
but  as  precipitated  from  the  mercurial  solution,  which  itself  yields  a 
precipitate  with  ammonia,  it  is  soluble  with  difficulty  in  that  alkali, 
and,  unless  very  large  excess  of  the  alkali  be  added,  is  soon  replaced 
by  a  white,  granular  deposit. 

1.  ^-g-jj-  grain  of  corrosive  sublimate,  in  one  grain  of  water,  yields 
a  very  copious,  white,  curdy  precipitate. 

23 


354  MERCURY. 

2.  Ywww  gi'ai^  yields  a  quite  good  precipitate,  which,  in  the  mixture, 

dissolves  with  difficulty  in  ammonia. 

3.  Yohro  gi'ain  :  a  good  deposit,  which  quickly  disappears  on  the 

addition  of  ammonia. 

4.  -g-Q.Voo"  gi^aiu  yields  a  quite  fair  precipitate. 

5.  YTo^.ToT  grain  :  a  very  satisfactory  turbidity. 

6.  .^-^-^-^  grain  yields  a  perceptible  cloudiness. 

This  reagent  is  simply  for  the  purpose  of  detecting  the  presence 
of  the  chlorine  of  the  corrosive  sublimate.  The  reaction  of  the 
reagent  is,  of  course,  common  to  solutions  of  all  soluble  chlorides  and 
of  free  hydrochloric  acid.  If,  however,  it  be  shown  by  any  of  the 
other  tests  that  the  solution  also  contains  mercury,  then  it  follows, 
providing  the  solution  is  not  a  complex  mixture,  that  the  metal 
existed  as  corrosive  sublimate,  since  this  is  its  only  soluble  chloride. 

Other  Reagents. — The  mercury  from  solutions  of  corrosive 
sublimate  may  be  precipitated,  in  a  state  of  combination,  by  several 
reagents  other  than  those  already  described,  but  the  reactions  of  these 
are  much  less  delicate  and  characteristic  than  those  already  considered. 
A  few  of  these  tests,  however,  may  be  very  briefly  mentioned. 

Potassium  ferrocyanide  produces  in  solutions  of  the  mercurial 
compound  a  dirty-white  precipitate,  which  is  soluble  in  excess  of 
the  precipitant.  One  grain  of  a  1-lOOth  solution  of  the  salt  yields 
a  very  copious  precipitate;  and  a  similar  quantity  of  a  1-lOOOth 
solution,  a  quite  good  deposit.  This  is  about  the  limit  of  the  reaction 
of  the  test  for  one  grain  of  the  solution. 

Potassium  ferricyanide  throws  down  from  aqueous  solutions  of 
the  salt  a  greenish-yellow,  amorphous  precipitate,  which  is  insoluble 
in  excess  of  the  precipitant.  One  grain  of  a  1-1 000th  solution  of 
the  mercurial  compound  yields  a  quite  good  precipitate ;  a  similar 
quantity  of  a  l-5000th  solution  yields  only  a  slight  turbidity. 

Potassium  chromate  produces  in  quite  strong  solutions  of  the  salt 
a  greenish -yellow  precipitate;  but  the  dichromate  occasions  no  visible 
reaction. 

Separation  from  Organic  Mixtures. 

Since  corrosive  sublimate  is  readily  precipitated,  with  more  or 
less  decomposition,  by  various  animal  and  vegetable  principles,  much 
of  the  poison,  when  added  to  mixtures  of  this  kind,  may  be  present 
in  a  form  insoluble  in  water.     Under  these  circumstances,  however, 


RECOVERY    FROM    ORGANIC    MIXTURES.  356 

.<;iilTit'ic'Mt  of  tlie  inorciirv  to  he  detected  by  the  ordinary  reagents  will 
usually  remain  in  .solution,  even  in  quite  complex  mixtures,  and  after 
standing  for  long  periods.  "We  find  that  the  solid  coagulum  result- 
ing from  the  precipitation  of  the  poison  with  albumen,  which  is  one 
of  the  most  insoluble  compounds  of  this  kind,  when  washed  and 
dried,  even  to  a  horny  mass,  still  yields  up  some  of  the  mercurial 
com})ound  on  digestion  with  even  cold  water ;  more  of  it  to  hot  water; 
and  still  more  when  boiled  with  water  acidulated  with  hydrochloric 
acid. 

Suspected  Solutions, — Any  precipitate  or  mechanically  suspended 
matter  present  is  separated  from  the  suspected  solution  by  a  filter, 
and  examined  for  any  solid  particles  of  the  poison,  then  washed  with 
warm  water,  and  reserved  for  future  examination,  if  necessary.  A 
portion  of  the  clear  liquid  may  then  be  acidulated  with  hydrochloric 
acid  and  boiled  with  a  small  slip  of  bright  copper-foil.  If  the  cop- 
per quickly  receives  a  metallic  coating,  it  is  removed  from  the  liquid, 
and  other  and  larger  slips  of  the  metal  consecutively  added,  as  long 
as  they  acquire  a  deposit.  If  the  deposit  thus  obtained  consists  of 
mercury,  it  will  usually  present  a  grayish-white  appearance,  and 
acquire  a  bright  silvery  lustre  when  gently  rubbed  with  the  finger 
or  any  other  soft  body.  The  coated  copper  is  then -washed  in  alcohol 
or  ether,  dried  at  a  moderate  temperature,  one  or  more  of  the  slips 
heated  in  an  appropriate  reduction-tube,  and  any  sublimate  obtained 
examined  by  a  low  power  of  the  microscope. 

If  the  method  now  described  yields  positive  results,  these  may 
be  confirmed  by  examining  other  portions  of  the  suspected  liquid 
by  some  of  the  other  tests  for  the  poison;  this,  however,  is  not  really 
necessary,  at  least  so  far  as  the  presence  of  mercury  is  concerned.  A 
portion  of  the  liquid  should  be  concentrated  to  a  small  volume,  and 
allowed  to  stand  in  a  cool  place  for  some  hours,  or  longer  if  necessary, 
in  order  that  the  poison,  if  present,  may  separate  in  its  crystalline 
state.  Any  crystals  thus  obtained,  after  being  carefully  washed,  are 
dissolved  in  a  small  quantity  of  water,  and  a  portion  of  the  solution 
tested  for  chlorine  by  silver  nitrate. 

Should  the  copper  test,  after  prolonged  heating  and  concentration 
of  the  liquid,  fail  to  reveal  the  presence  of  mercury,  it  is  quite  certain 
that  the  other  tests  for  this  metal  would  also  fail,  since  they  are  much 
less  delicate  in  their  reaction  than  the  former.  Under  these  circum- 
stances, any  organic  solids  separated  from  the  suspected  liquid,  by 


356  MEECURY. 

filtration,  are  boiled  for  about  ten  minutes  with  pure  water,  or,  better 
still,  so  far  as  the  recovery  of  mercury  is  concerned,  with  water 
strongly  acidulated  with  hydrochloric  acid ;  the  cooled  liquid  is  then 
filtered,  and  the  filtrate  examined  by  the  copper  test,  in  the  manner 
above  described.  It  is  obvious  that  the  employment  of  hydrochloric 
acid  in  the  preparation  of  the  liquid  will,  in  the  event  of  the  de- 
tection of  mercury,  preclude  the  possibility  of  proving  that  the  metal 
existed  as  a  chloride,  at  least  so  far  as  the  liquid  under  examination 
is  concerned. 

Another  method  for  the  recovery  of  corrosive  sublimate  from 
organic  liquids  is  to  agitate  violently  the  concentrated  liquid,  for 
some  minutes,  in  a  small  bottle  or  a  stout  test-tube,  with  about  twice 
its  volume  of  pure  commercial  ether,  in  which,  as  we  have  already 
seen,  the  salt  is  freely  soluble.  When  the  liquids  have  completely 
separated,  which  will  usually  require  a  repose  of  only  a  few  minutes, 
the  ethereal  fluid  is  carefully  decanted  into  a  watch-glass,  and  allowed 
to  evaporate  spontaneously.  Any  saline  residue  thus  obtained  is 
examined  in  the  usual  manner,  a  portion  of  it  being  first  examined 
by  some  of  the  tests  for  the  poison  in  its  solid  state.  In  the  appli- 
cation of  this  method  it  should  be  borne  in  mind  that  ether  does 
not  extract  the  whole  of  the  salt  from  its  aqueous  solutions. 

Vomited  matte7's.— The  matters  ejected  from  the  stomach  may  be 
examined  in  the  same  manner  as  just  described  for  suspected  solu- 
tions. If  an  antidote,  such  as  white  of  egg  or  gluten,  was  admin- 
istered, the  organic  solids  of  the  vomited  matters  may  require  long 
boiling  with  water  strongly  acidulated  with  hydrochloric  acid,  for 
the  complete  separation  of  the  poison. 

Contents  of  the  Stomach. — As  corrosive  sublimate  is  readily  solu- 
ble, it  is  not  often  found  in  its  solid  state  in  the  stomach :  however, 
this  examination  should  not  be  omitted.  The  mass  is  then  stirred 
with  sufficient  water  to  make  it  quite  liquid,  the  mixture  gently  heated 
for  some  time  on  a  water-bath,  the  cooled  liquid  filtered,  and  the 
solids  on  the  filter  well  washed  with  pure  water,  the  washings  being 
collected  with  the  first  filtrate.  The  filter,  with  its  contents,  should  be 
reserved.  The  clear  liquid  is  then  concentrated  to  an  appropriate 
volume,  and,  if  necessary,  again  filtered. 

A  portion  of  the  filtrate  thus  obtained  is  acidulated  with  hydro- 
chloric acid,  and  boiled  with  a  very  small  slip  of  bright  copper- 
foil.    If  this  fails  to  receive  a  metallic  coating,  the  application  of  the 


RECOVKRY    FROM    ORGANIC    MIXTURES.  357 

heat  sliould  bo  coiitiiiiicd  until  the  liquid  is  evajwrated  to  near  dry- 
ness, before  coneliidiiig  that  the  jmi.son  is  entirely  absent.  On  the 
other  hand,  if  the  copper  quickly  receives  a  metallic  deposit,  it  is 
removed  from  the  liquid,  and  other  slips  of  the  metal  added  as  long 
as  thev  become  coated.  The  mercurial  deposit,  as  already  pointed 
out,  is  reiidily  distino;nished  from  that  produced  by  arsenic,  antimony, 
and  most  other  metals  that  are  thus  deposited,  by  its  bright  silvery 
ai>pearance,  at  least  when  rubbed.  The  coated  copper  is  thoroughly 
washed  in  alcohol  or  ether,  dried,  then  heated  in  a  reduction-tube, 
and  any  sublimate  thus  obtained  examined  by  the  microscope. 

Another  portion  of  the  filtrate  may  be  acidulated  with  hydro- 
chloric acid,  and  treated  with  excess  of  a  solution  of  stannous  chlo- 
ride, when,  if  it  yields  a  dark  gray  precipitate,  the  mixture  is  gently 
heated  until  the  precipitate  has  completely  subsided  ;  the  supernatant 
fluid  is  then  decanted,  the  residue  washed  with  hot  water,  then  boiled 
with  a  little  water  strongly  acidulated  with  pure  hydrochloric  acid, 
which  will  cause  any  finely  divided  mercury  present  to  collect  into 
comparatively  large  globules.  It  must  be  remembered  that  various 
organic  solutions  yield  with  the  tin  reagent  a  white  precipitate, 
which  may  more  or  less  conceal  the  color  of  the  mercurial  deposit. 
Under  these  circumstances,  the  precipitate  is  boiled  for  some  time 
with  a  strong  solution  of  caustic  potash,  which  will  dissolve  the 
organic  matter,  leaving  the  mercury  in  the  form  of  a  grayish-black 
powder.  This  is  then  boiled  with  a  little  diluted  hydrochloric  acid, 
in  the  manner  just  described. 

If  a  portion  of  the  filtrate  be  acidulated  with  hydrochloric  acid 
and  treated  with  sulphuretted  hydrogen  gas,  any  of  the  poison  pres- 
ent will  give  rise  to  sulphide  of  mercury,  which  will  be  thrown 
down  as  a  black  precipitate,  at  least  if  excess  of  the  reagent  has  been 
employed.  After  the  precipitate  has  completely  subsided,  it  may  be 
collected  on  a  filter,  washed,  and  then  dried.  Its  mercurial  nature 
may  be  established  l)y  mixing  it  with  several  times  its  volume  of 
recently  ignited  sodium  carbonate  and  heating  the  mixture  in  a 
reduction-tube,  when  it  will  undergo  decomposition  with  the  produc- 
tion of  a  globular  sublimate  of  metallic  mercury,  readily  identified 
by  means  of  the  microscope. 

The  positive  reaction  of  either  of  the  foregoing  tests  would,  of 
course,  simply  indicate  the  presence  of  the  mercury  of  the  corrosive 
sublimate.     For  the  purpose  of  showing  the  presence  of  the  chlorine, 


358  MERCUEY. 

it  is  best  to  agitate  a  portion  of  the  filtrate  with  ether,  in  the  manner 
already  directed,  then  allow  the  ethereal  solution  to  evaporate  spon- 
taneously, dissolve  the  residue  in  a  small  quantity  of  warm  water, 
and  treat  the  solution  with  silver  nitrate.  As  the  alkaline  chlorides 
are  insoluble  in  ether,  the  detection  of  chlorine  under  these  circum- 
stances would  not  be  open  to  the  objection  that  would  hold  if  the 
silver  reagent  were  applied  directly  to  the  original  filtrate  :  especially 
will  this  objection  be  guarded  against  if  the  ethereal  liquid,  on  evapo- 
ration, leave  the  poison  in  its  crystalline  state. 

Should  the  methods  already  given  fail  to  reveal  the  presence  of 
mercury  in  the  filtrate,  then  the  organic  solids  left  upon  the  filter 
may  be  examined.  For  this  purpose  the  mass  is  transferred  to  a 
porcelain  dish,  the  solids  cut  into  small  pieces,  and  boiled  for  about 
twenty  minutes  with  pure  water,  the  mixture  being  frequently  stirred 
by  means  of  a  glass  rod.  When  the  mixture  has  cooled,  the  liquid 
portion  is  separated  by  a  filter,  the  filtrate  concentrated  to  a  small 
volume,  and  then  examined  in  the  manner  before  directed  for  the 
first  filtrate.  Instead  of  boiling  the  organic  solids  with  pure  water, 
they  may  be  boiled  with  water  containing  hydrochloric  acid  until 
they  are  entirely  disintegrated.  If,  however,  this  method  be  em- 
ployed, the  presence  of  the  chlorine  of  the  corrosive  sublimate  can- 
not be  established. 

Another  method  for  the  examination  of  the  above  organic  solids 
is  to  boil  the  mass  with  a  somewhat  concentrated  solution  of  potas- 
sium hydrate  until  the  solids  are  entirely  decomposed,  and  then  treat 
the  mixture  with  a  solution  of  stannous  chloride,  the  heat  being  con- 
tinued for  some  little  time  after  the  addition  of  the  tin  reagent.  Any- 
dark  gray  precipitate  thus  obtained  is  carefully  collected,  washed,  and 
examined  in  the  manner  already  described. 

From  the  Tissues. — If  there  has  been  a  failure  to  detect  corrosive 
sublimate  under  one  or  other  of  the  conditions  now  described,  it  will 
no  longer  be  possible  to  show  the  presence  of  the  poison  as  a  whole ; 
but  the  presence  of  the  absorbed  mercury  may  be  shown  in  some 
of  the  soft  tissues  of  the  body.  For  the  recovery  of  the  absorbed 
metal  various  methods  have  been  advised.  The  finely  divided 
tissue,  as  about  ten  ounces  of  the  liver,  may  be  made  into  a  thin 
paste  with  water,  containing  about  one-sixth  of  its  volume  of  pure 
hydrochloric  acid,  and  the  whole  heated  at  about  the  boiling  tem- 
perature until  the  organic  solids  are  completely  disintegrated,  which 


SEPARATION    FIIOM    THE   TISSUES.  369 

will  usually  require  about  two  hours.  The  mass  is  theu  allowed  to 
cool,  transfjerred  to  a  linen  strainer,  the  strained  liquid  filtered,  and 
then  conecntrated  to  a  comparatively  small  volume.  A  portion  of 
the  liquid  may  now  be  heated  to  the  boiling  temperature,  and  ex- 
amined by  the  copper  test,  employing  at  first  only  a  very  minute  slip 
of  the  metal.  In  applying  this  test,  it  should  be  remembered  that 
the  copper,  after  prolonged  heating,  may  acquire  a  very  distinct  stain 
or  tarnish,  even  in  the  absence  of  mercury  or  of  any  other  metal. 
Before  heating  the  copper  in  a  reduction-tube  it  should  be  very 
thoroughly  washed,  first  in  water  containing  a  little  ammonia. 
Should  the  first  portion  of  liquid  examined  fail  to  reveal  the  presence 
of  mercury,  then  another  and  larger  portion,  or  even  the  whole  of 
the  remaining  liquid,  should  be  examined  in  a  similar  manner. 

The. copper  test  will  serve  to  recover  very  minute  quantities  of 
mercury  from  very  complex  organic  liquids.  A  portion  of  a  human 
liver,  free  from  mercury,  was  boiled  with  diluted  hydrochloric  acid 
in  the  manner  just  described,  and  the  liquid  strained.  To  one  hun- 
dred grain-measures  of  the  strained  fluid  the  1-lOOOth  of  a  grain 
of  corrosive  sublimate  was  added, — the  poison  then  being  under  a 
dilution  of  100,000  times  its  w^eight  of  the  organic  liquid, — and  the 
mixture  boiled  with  a  very  small  slip  of  bright  copper-foil.  After 
a  little  time  the  copper  received  a  very  distinct  metallic  stain,  and, 
when  washed,  dried,  and  heated  in  a  small  reduction-tube,  yielded  a 
sublimate  which,  under  the  microscope,  was  found  to  contain  over 
one  hundred  characteristic  globules  of  mercury. 

Should  the  examination  of  the  first  portion  of  the  above  liquid 
indicate  the  presence  of  mercury,  and  it  be  desired  to  pursue  the  in- 
vestigation, another  portion  may  be  treated  wnth  excess  of  stannous 
chloride,  and  gently  warmed,  until  the  precipitate  has  completely 
deposited.  The  precipitate  is  then  collected,  w^ashed,  and  boiled  in 
a  porcelain  evaporating-dish  with  a  solution  of  potassium  hydrate 
until  the  organic  matter  is  dissolved  and  the  residue  assumes  a  dark 
gray  color.  The  clear  supernatant  liquid  is  then  decanted,  and  the 
residue  repeatedly  washed  with  hot  water,  then  boiled  wuth  hydro- 
chloi'ic  acid,  which  will  cause  any  finely  divided  mercury  present,  if 
entirely  free  from  foreign  matter,  to  coalesce  into  globules. 

Another,  and  in  some  cases  preferable,  method  for  breaking  up 
the  animal  tissues  is  by  means  of  hydrochloric  acid  and  potassium 
chlorate,  in  the  manner  described  for  the  recovery  of  absorbed  arsenic. 


360  MERCURY. 

The  finely  divided  tissue  is  treated  with  about  one-fourth  of  its  weight 
of  pure  concentrated  hydrochloric  acid,  and  the  whole  made  into  a 
thin  paste  by  the  addition  of  water.  The  mixture  is  then  heated  to 
about  the  boiling  temperature,  and  small  quantities  of  powdered  potas- 
sium chlorate  occasionally  added  until  the  mass  becomes  perfectly 
homogeneous,  after  which  it  is  kept  at  a  gentle  heat  until  the  odor 
of  chlorine  has  entirely  disappeared.  The  mixture  is  now  allowed 
to  cool,  the  liquid  filtered,  and  the  solid  matters  on  the  filter  well 
washed  with  hot  water.  The  filtrate  may  now  be  partially  neutral- 
ized with  pure  sodium  carbonate,  and  concentrated  until  its  volume 
is  about  three  times  that  of  the  hydrochloric  acid  employed  in  the 
destruction  of  the  organic  matter. 

The  liquid  tluis  obtained,  after  filtration  if  necessary,  is  exposed 
for  several  hours  to  a  slow  stream  of  sulphuretted  hydrogen  gas,  then 
gently  heated,  and  allowed  to  stand  in  a  moderately  warm  place  for 
about  fifteen  hours.  Any  mercury  present  will  now  be  in  the  pre- 
cipitate, in  the  form  of  the  black  sulphide,  together  with  more  or  less 
organic  matter,  the  color  of  which  may  disguise  that  of  the  mercurial 
compound.  The  precipitate  is  collected  upon  a  small  filter,  well 
washed,  and  then  transferred  to  a  porcelain  dish,  treated  with  a  pro- 
portionate quantity  of  concentrated  hydrochloric  acid,  and  pure  nitric 
acid  added  drop  by  drop  until  complete  solution  has  taken  place.  By 
this  treatment  with  the  mixed  acids  the  mercury  of  the  mercurial 
sulphide  will  be  dissolved  to  mercuric  chloride,  while  the  sulphur  will 
be  eliminated  as  a  yellow  adherent  mass,  which  as  it  forms  should  be 
removed  by  means  of  a  glass  rod.  On  now  cautiously  evaporating 
the  solution  to  dryness  on  a  water-bath,  the  mercuric  chloride  will 
be  left  as  a  white  crystalline  mass;  if  the  eliminated  sulphur  was  not 
removed  from  the  mixture,  the  residue  may  consist  largely  of  mer- 
curic sulphate. 

A  portion  of  the  saline  residue  thus  obtained  may  be  tested  for 
the  poison  in  its  solid  state,  and  another  portion  dissolved  in  a  small 
quantity  of  water,  and  the  solution  examined  by  the  copper  test.  If 
the  addition  of  water  produces  an  insoluble  yellow  sulphate  of  mer- 
cury, its  solution  may  be  readily  effected  by  the  addition  of  a  drop 
or  two  of  hydrochloric  acid. 

From  the  Urine. — About  300  c.c,  or  twelve  fluid -ounces,  of  the 
urine  are  strongly  acidulated  with  hydrochloric  acid,  evaporated  to  a 
small  volume,  filtered,  the  filtrate  boiled  with  a  small  slip  of  bright 


FAILURE   TO    DETECT.  3G1 

copper- foil,  and  the  latter  waslied,  dried,  and  examined  in  the  usual 
iiiaiuier.  Another  method  for  tiie  examination  of  this  fluid  is  to 
croncentrate  it  to  near  dryness,  and  then  destroy  the  organic  matter 
by  means  of  hydrochloric  acid  and  potassium  chlorate,  in  the  manner 
described  for  the  recovery  of  the  poison  from  the  tissues.  If  the 
first  of  these  methods  be  ad()j)ted  and  there  is  a  failure  to  detect  the 
metal,  any  solids  separated  by  filtration  should  be  examined. 

Dr.  Thudichum  remarks  {Pathology  of  the  Urine,  408)  that  in 
all  cases  where  the  urine  contains  mercury  there  is  at  the  same  time 
a  peculiar  albuminous  substance  present  in  it,  which  with  nitric  acid 
yields  a  faint  reaction  of  albumen.  A  substance  is  also  present 
having  the  reactions  of  sugar.  In  some  cases  of  mercurial  ism,  he 
adds,  the  metal  only  appeared  in  the  urine  at  intervals,  even  where 
the  symptoms  had  undergone  no  remission. 

Failure  to  detect  the  Poisox. — It  has  not  unfrequently 
happened  in  acute  corrosive  sublimate  poisoning  that  there  was  a 
failure  to  detect  the  poison  in  any  part  of  the  dead  body.  In  a 
case  quoted  by  Dr.  Beck  [Med.  Jur.,  ii.  638),  in  which  a  woman  had 
poisoned  herself  with  this  substance,  not  a  trace  of  the  poison  was 
found  either  in  the  matters  vomited  during  life  or  in  the  contents 
of  the  stomach  after  death.  So,  also,  in  a  case  cited  by  Wharton 
and  Stille  (Med.  Jur.,  538),  none  of  the  poison  was  detected  in  the 
stomach  and  intestines  of  a  young  man  who  had  taken  three  drachms 
of  corrosive  sublimate,  and  died  from  its  effects  on  the  sixth  day.  In 
another  instance,  recorded  by  Dr.  Taylor  (On  Poisons,  471),  in  which 
two  drachms  were  swallowed,  and  death  occurred  on  the  fourth  day, 
a  chemical  examination  of  the  stomach,  blood,  and  tissues  failed  to 
reveal  the  presence  of  mercury. 

According  to  the  observations  of  I.  L.  Orfila,  absorbed  mercury 
is  eliminated  from  the  system  chiefly  by  means  of  the  kidneys.  In 
examining  the  urine  of  patients  treated  with  mercurial  preparations, 
he  found  the  metal  five  days  after  it  had  ceased  to  be  taken,  but  in 
eight  days  it  was  no  longer  discovered.  In  experiments  upon  dogs, 
he  found  the  metal  in  the  tissue  of  the  stomach  and  liver  of  some  of 
the  animals  as  late  as  the  eighteenth  day,  but  in  others,  similarly 
treated,  it  had  entirely  disappeared.  [Orfila'' s  Toxicologie,  1852,  i. 
680.) 

When  mercury  remains  in  the  body  at  the  time  of  death,  it,  like 


362  MERCURY. 

arsenic,  may  be  recovered  after  very  long  periods.  In  a  case  of  cor- 
rosive sublimate  poisoning,  which  we  examined  some  years  since,  and 
in  which  death  occurred  on  the  fourth  day,  the  metal  was  readily 
detected  in  the  stomach  and  liver  of  the  body  after  it  had  been  buried 
nine  months:  none  of  the  other  organs  were  chemically  examined. 
It  need  hardly  be  remarked  that,  since  mercurial  preparations  are  so 
frequently  taken  medicinally,  the  detection  of  minute  traces  of  the 
metal  in  the  dead  body  would  not  in  itself  be  any  evidence  that  it 
was  the  cause  of  death. 

According  to  the  researches  of  J.  G.  Smith,  Ph.G.  [Amer.  Jour. 
Pharm.,  Aug.  1877,  397),  commercial  corrosive  sublimate  is  fre- 
quently contaminated  with  minute  quantities  of  arsenic,  most  likely 
derived  from  the  sulphuric  acid  used  in  preparing  the  mercuric  sul- 
phate, from  which  afterward  tlie  mercuric  chloride  is  sublimed.  In 
five  samples  of  the  salt  in  which  the  arsenic  was  determined  quan- 
titatively, the  proportion  of  this  metal,  expressed  as  arsenic  oxide, 
varied  from  0,033  to  0.096  per  cent. 

Quantitative  Analysis. — The  quantity  of  corrosive  sublimate 
present  in  a  solution  of  the  salt  may  be  readily  estimated  by  precipi- 
tating the  metal  as  mercuric  sulphide.  For  this  purpose,  the  solution, 
acidulated  with  hydrochloric  acid,  is  saturated  with  a  slow  stream  of 
washed  sulphuretted  hydrogen  gas,  after  which  it  is  allowed  to  stand 
in  a  moderately  warm  place  until  the  precipitate  has  completely  sub- 
sided ;  the  precipitate  is  then  collected  on  a  small  filter  of  known 
weight,  washed  with  pure  water  until  the  washings  no  longer  have 
an  acid  reaction,  dried  on  a  water-bath  at  100°  C.  (212°  F.),  and 
weighed.  One  hundred  parts  by  weight  of  the  dried  sulphide  cor- 
respond to  116.81  parts  of  anhydrous  corrosive  sublimate,  or  86.20 
parts  of  metallic  mercury. 

If  in  the  application  of  the  tin  test  a  known  quantity  of  the 
mercurial  solution  was  employed,  any  globules  of  metallic  mercury 
obtained  may  be  carefully  washed,  dried,  and  weighed.  One  hundred 
parts  by  weight  of  the  pure  metal  represent  135.5  parts  of  corrosive 
sublimate. 


LEAD. 


363 


CHAPTER   TIL 

LEAD,   COPPER,  ZINC. 
Section  1. — Lead. 

History  and  Chemical  Nature.— Lead  is  one  of  the  elementary 
metals.  Its  symbol  is  Pb ;  its  atomic  weight  207 ;  and  its  density 
11.44.  It  is  fonnd  in  nature  associated  with  several  other  elements, 
but  it  occurs  principally  as  sulphide  of  lead,  or  galena.  Lead  has 
a  bluish-gray  color  and  a  strong  metallic  lustre;  it  is  quite  soft,  being 
easily  scratched  by  the  finger-nail,  and  leaves  a  well-known  mark 
upon  white  paper.  It  is  very  malleable,  and  fuses  at  about  315.5° 
C.  (600°  F.). 

In  its  pure  state  lead  is  unacted  upon  by  pure  water.  But  if 
air  be  present  in  the  liquid,  or  its  surface  be  freely  exposed  to  the 
action  of  the  atmosphere,  the  metal  rapidly  becomes  corroded,  and 
gives  rise  to  oxide  of  lead,  which  partly  unites  with  water  and  partly 
with  carbonic  acid,  forming  a  hydrated  oxycarbonate  of  lead.  This 
compound  partly  deposits  upon  the  lead  as  silky  scales  or  falls  as  a 
precipitate,  while  a  portion  remains  mechanically  suspended  in  the 
liquid ;  at  the  same  time  some  little  of  the  compound  becomes  dis- 
solved. When,  however,  the  water  holds  in  solution  certain  salts, 
such  as  the  carbonates,  sulphates,  or  phosphates,  an  insoluble  crust 
of  lead  salt  slowly  deposits  upon  the  metal  and  protects  it  from 
further  action,  and  thus  none  of  the  lead  is  dissolved.  On  the  other 
hand,  the  presence  of  chlorides  and  of  nitrates  increases  the  corrosive 
action  of  water.  Dr.  Frankland  found  that  water  which  acted  on 
lead  lost  this  power  after  passing  through  a  filter  of  animal  charcoal, 
owing  to  a  minute  quantity  of  calcium  phosphate  passing  into  the 
water  from  the  charcoal.     [Chem.  News,  Dec.  1868,  296.) 

Lead  is  readily  soluble  in  diluted  nitric  acid,  especially  upon 
the  application  of  heat,  with  the  formation  of  lead  nitrate,  and  the 


364  LEAD. 

evolution  of  nitrous  fumes.  Cold  diluted  sulphuric  acid  fails  to 
dissolve  it,  but  the  hot  concentrated  acid  dissolves  it  to  lead  sulphate, 
with  the  evolution  of  sulphurous  oxide  gas.  Hydrochloric  acid, 
even  under  the  application  of  heat,  has  but  little  action  upon  the 
metal.  Heated  on  charcoal  before  the  blow-pipe  flame,  it  gives  rise 
to  a  yellow  or  brownish  incrustation  of  oxide  of  lead. 

Physiological  Effects. — In  its  metallic  state  lead  seems  to  be  inert. 
But  all  the  compounds  of  the  metal  that  are  soluble  in  water  or  in 
the  animal  juices  are  more  or  less  poisonous.  Acute  poisoning  by 
the  preparations  of  lead  has  been  of  rare  occurrence,  and  has  chiefly 
been  the  result  of  accident. 

Of  the  salts  of  lead,  the  acetate,  or  sugar  of  lead,  is  one  of  the 
most  active,  and  has  more  frequently  been  taken  as  a  poison  than 
any  of  the  other  compounds.  This  salt,  however,  is  poisonous  only 
when  taken  in  large  quantity.  Van  Swieten  mentions  an  instance 
in  which  it  was  given  to  the  amount  of  a  drachm  daily  for  ten  days 
before  it  caused  any  material  symptom.  (Christison,  On  Poiscms,  430.) 
Cases  are  not  wanting,  however,  in  which  it  produced  speedy  and 
violent  symptoms,  and  even  death. 

Acetate  of  Lead. 

Symptoms. — AThen  an  overdose  of  acetate  of  lead  is  swallowed, 
the  patient  usually  experiences  at  first  a  nauseous  metallic  taste  in 
the  mouth,  with  a  sense  of  constriction  or  burning  heat  in  the  fauces 
and  epigastrium.  These  effects  are  followed,  sooner  or  later,  by 
severe  gastric  and  abdominal  pains,  which  are  generally  relieved,  but 
sometimes  increased,  by  pressure ;  sometimes  the  pain  is  constant,  at 
other  times  intermittent.  There  is  also  nausea,  and  sometimes  fre- 
quent vomiting  of  a  yellowish  or  blackish  liquid ;  in  some  instances 
the  vomiting  has  been  very  slight.  The  thirst  is  frequently  very 
urgent ;  the  skin  cold,  but  sometimes  hot,  and  generally  covered  by  a 
clammv  perspiration ;  the  countenance  anxious  ;  the  strength  greatly 
prostrated  ;  the  pulse  slow  and  feeble,  but  often  accelerated.  In  some 
instances  there  has  been  severe  and  even  bloody  purging ;  but  gen- 
erally the  bowels  are  obstinately  constipated,  there  being  either  no 
discharge  or  the  matters  passed  being  hard,  dry,  and  black  and  their 
discharge  attended  with  pain.  Sometimes  the  limbs  become  affected 
with  spasms  and  a  sense  of  constriction.  The  urine  is  usually 
diminished  in  quantity.     The  intellect  generally  remains  clear. 


ClIliOMlC   POISONING. 


365 


Dr.  MascliUa  relates  the  ca.se  of*  an  a^ed  man  who  liad  been  ill 
for  some  days,  and  when  first  seen  by  a  physician  was  suffering  from 
yellowness  of  the  conjunctiva,  loss  of  aj^petite,  eructations,  accumu- 
lation of  phlejiin  on  the  chest,  and  attacks  of  giddiness.  The  evac- 
uations were  normal,  the  thirst  not  increased,  pulse  80  to  90,  the 
tongue  coated,  and  the  man  felt  weaU.  On  the  following  day  the 
weakness  and  other  symptoms  had  increased  ;  but  under  the  ad- 
ministration of  tonics  the  patient  became  better.  On  the  evening  of 
the  fourth  day,  however,  he  became  worse;  his  eyes  were  fixed,  his 
breathing  short  and  rattling,  pulse  weak,  the  extremities  cold,  and 
death  shortly  ensued.  Lead  in  large  quantity  was  found  in  the 
contents  of  the  stomach.  The  quantity  of  sugar  of  lead  taken  just 
before  the  increased  symptoms  preceding  death  a])peared  was  said  to 
have  been  20.12  grammes.     [Med.-Chir.  Rev.,  1872,  265.) 

A  case  is  reported  in  which  the  death  of  an  infant  was  caused  by 
the  use  of  a  lotion  of  lead  acetate  applied  for  sore  nipples.  The 
mother  omitted  to  wash  the  lotion  off  before  putting  the  child  to  the 
breast.  It  was  seized  with  violent  colic,  and  died  in  a  few  days 
with  the  usual  symptoms  of  lead  poisoning. 

Dr.  von  Linstow  reports  {Viert.f.  Gericht.  Med.,  Jan.  1874)  two 
cases  of  fatal  poisoning  by  lead  chromate,  which  occurred  in  children 
aged  respectively  one  and  three-quarters  and  three  and  a  half  years, 
caused  by  sucking  some  pastry  colored  by  chrome  yellow.  Several 
hours  after  the  poison  had  been  taken,  both  children  were  taken 
with  vomiting,  which  lasted  several  hours,  the  matters  vomited 
having  a  yellow  color.  There  was  great  prostration  and  extreme 
thirst,  but  no  diarrhoea  nor  pain.  On  the  second  day  both  had  a 
hot  and  red  countenance,  and  were  stupid.  The  younger,  about 
twenty-four  hours  after  the  commencement  of  the  symptoms,  had  a 
slight  diarrhoea  and  convulsions,  which  continued  until  death,  which 
took  place  in  forty-eight  hours.  On  the  third  day  an  erythema- 
tous eruption  appeared  on  the  chest  and  abdomen  of  the  elder,  and 
he  was  dull  and  stupid.  On  the  fourth  day  the  pulse  and  respira- 
tion became  irregular,  the  breath  extremely  fetid,  stupor  and  un- 
consciousness supervened ;  and  the  patient  died  five  days  after  the 
ingestion  of  the  poison.  The  quantity  taken  in  each  case  was  be- 
lieved to  be  between  the  l-5th  and  the  l-6th  of  a  grain  of  the  lead 
compound. 

Chronic  Poisoning .—li  is  well  known  that  the  frequently  re- 


366  LEAD. 

peated  introduction  of  even  very  minute  quantities  of  any  of  the 
preparations  of  lead  into  the  system  may  after  a  time  induce  serious 
symptoms.  Under  these  circumstances,  the  patient  experiences  gen- 
eral depression,  loss  of  appetite,  a  metallic  taste  in  the  mouth,  and 
generally  great  thirst.  The  throat  becomes  dry,  the  breath  fetid, 
the  countenance  dull  and  anxious,  the  skin  dry  and  of  a  dull  yellow 
color,  the  bowels  constipated,  and  the  urine  generally  diminished. 
At  the  same  time  a  blue  line  forms  along  the  margins  of  the  gums ; 
and  there  is  more  or  less  uneasiness  or  pain  in  the  abdomen.  As  the 
case  advances,  the  pain  in  the  abdomen  becomes  very  severe,  and 
more  or  less  constant :  the  walls  of  this  cavity  are  generally  hard 
and  depressed.  These  effects  are  frequently  followed  by  sharp  pains 
in  the  extremities,  muscular  emaciation,  and  paralysis. 

A  remarkable  series  of  cases  of  lead  poisoning  occurred  a  few 
years  since  from  the  use  of  flour  from  a  mill  in  which  the  mill- 
stones had  been  repaired  by  filling  the  defective  parts  with  lead. 
Of  four  hundred  and  twelve  persons  who  suffered  from  the  use  of 
the  flour,  thirty  died.  {Med.  Times  and  Gaz.,  May,  1878.)  Other 
instances  similar  to  this  have  been  reported. 

Within  recent  years  a  number  of  cases  of  lead  poisoning  have 
occurred  from  the  use  of  canned  fruits  preserved  in  tinned  cans 
alloyed  with  lead.  In  a  case  of  this  kind  reported  by  Dr.  Magru- 
der  {Med.  News,  Sept.  1883,  261),  there  were  colic,  arthralgia,  and 
paralysis,  involving  first  the  extensors  of  the  wrist,  and  then  those 
of  the  lower  extremities,  and  extending  also  to  the  flexors  of  both. 
The  lead-cachexia  was  well  marked,  and  the  bluish  line  on  the  gums 
very  distinct. 

In  a  case  reported  by  Dr.  G.  A.  Kunkler,  the  external  appli- 
cation of  white-lead  to  a  scalded  surface,  as  a  dressing,  produced 
unmistakable  symptoms  of  lead  colic, — acute  abdominal  pain,  retrac- 
tion of  the  umbilicus,  constipation,  and  slight  discoloration  of  the 
gums.  {Med.-Chir.  Rev.,  Oct.  1857,  525.)  And  Dr.  G.  Johnson, 
of  London,  has  reported  (1875)  a  very  severe  case  of  chronic  lead 
poisoning  resulting  from  the  use  of  flahe-white,  composed  chiefly  of 
carbonate  of  lead,  as  a  cosmetic. 

When  Fatal. — In  a  case  quoted  by  Dr.  Beck,  a  soldier  who  swal- 
lowed an  unknown  quantity  of  acetate  of  lead  in  solution  was  soon 
seized  with  the  most  violent  symptoms,  indicative  of  gastric  inflam- 
mation, and  died  in  great  agony  at  the  end  of  three  days.     {Med. 


FATAL   QUANTITY.  307 

Jur.  i.  690.)  Dr.  Tiiylor  refers  to  two  cases  in  \vlii<-li  Goulard's 
extract— which  is  a  solution  of  the  subacetate  of  lead— was  taken  in 
unknown  quantity  by  two  children,  aj^ed  respectively  four  and  six 
years,  and  tluy  both  died  within  thirty-six  hours.  The  symptoms 
were  at  first  violent  vomiting  and  purging:  in  one  case  they  re- 
sembled those  of  Asiatic  cholera.  {Op.  cit.,  482.)  In  a  case  men- 
tioned by  Dr.  Christison  {On  Poisons,  430)  the  same  preparation  of 
lead  was  taken  in  unknown  quantity  by  a  soldier.  The  first  symp- 
toms could  not  be  ascertained,  but  on  the  second  day  he  was  affected 
with  loss  of  appetite,  paleness,  costiveness,  and  excessive  debility ; 
on  the  third  day  he  had  severe  colic,  drawing  in  of  the  abdomen, 
loss  of  voice,  cold  sweats,  locked  jaw,  and  violent  convulsions,  and 
expired  before  the  evening  of  the  same  day. 

Fatal  Quantity.— In  the  few  fatal  cases  of  acute  poisoning  by 
lead  acetate  that  have  occurred,  the  quantity  taken  could  not  be 
accurately  determined.  Instances  are  reported  in  which  doses  of 
about  an  ounce  were  taken  without  producing  any  very  serious  re- 
sults. On  the  other  hand,  a  case  is  quoted  by  Dr.  Christison  in 
which  two  doses  of  a  drachm  each  taken  by  a  man,  with  an  interval 
of  several  hours  between  the  doses,  produced  acute  pain  in  the  abdo- 
men, bilious  vomiting,  loss  of  speech,  delirium,  profuse  sweating, 
and  slow  pulse:  with  the  aid  of  treatment  the  patient  recovered. 
Two  cases  have  already  been  cited  in  each  of  which  about  the  l-5th 
of  a  grain  of  the  chro'mate  of  lead  proved  fatal  to  two  very  young 

children. 

Treatment. — In  acute  poisoning  by  the  acetate  of  lead,  the 
stomach  should  be  immediately  emptied  by  the  administration  of  an 
emetic  of  zinc  sulphate,  and  its  action  followed  by  large  draughts 
of  milk  containing  white  of  egg.  Various  chemical  antidotes  have 
been  proposed.  Among  these  the  most  useful  is  sulphuric  acid  in 
the  form  of  a  solution  of  magnesium  or  sodium  sulphate.  Either 
of  these  salts  would  decompose  the  lead  compound,  with  the  forma- 
tion of  insoluble  and  inert  lead  sulphate.  The  alkaline  sulphides 
have  also  been  recommended.  They  would  give  rise  to  the  insoluble 
sulphide  of  lead.  These  salts,  however,  are  in  themselves  poisonous 
in  large  doses,  and  their  use  as  antidotes  has  not  been  as  successful 
as  upon  chemical  grounds  might  have  been  expected.  The  hydrated 
sesquisulphide  of  iron  has  been  strongly  recommended  by  M.  Bou- 
chardat;   and    its   efficacy  has   been   recently  confirmed    in   a  case 


368  LEAD. 

reported  by  M.  Lepage.  As  this  compound  is  inert,  it  may  be  ad- 
ministered in  large  quantity.  The  alkaline  carbonates  are  inadmis- 
sible, as  they  would  give  rise  to  lead  carbonate,  which  is  equally 
poisonous  with  the  acetate  of  the  metal.  In  chronic  lead  poison- 
ing, M.  Rabuteau  strongly  advises  sodium  iodide  as  preferable  to  the 
potassium  salt. 

Post-mortem  Appearances. — In  the  case  already  cited  from 
Dr.  Beck,  the  mucous  membrane  of  the  stomach  was  found  abraded 
in  several  places,  particularly  near  the  pylorus ;  and  the  oesophagus, 
stomach,  duodenum,  mesentery,  liver,  and  spleen  were  in  a  state  of 
high  inflammation.  In  the  two  cases  mentioned  by  Dr.  Taylor,  the 
mucous  membrane  of  the  stomach  was  found  of  a  gray  color,  but 
otherwise  perfectly  healthy  ;  and  the  intestines  were  much  contracted. 
In  the  fatal  case  cited  by  Dr.  Christison,  the  lower  end  of  the  oesoph- 
agus, the  whole  stomach  and  duodenum,  part  of  the  jejunum,  and 
the  ascending  and  transverse  colon  were  found  much  inflamed  ;  and 
the  villous  coat  of  the  stomach  appeared  as  if  macerated. 

It  is  necessary  to  bear  in  mind  that  acetate  of  lead  has  caused 
death  without  leaving  any  well-marked  morbid  appearance  in  the 
body. 

In  the  two  cases  in  which  the  chromate  of  lead  proved  fatal,  the 
raucous  membrane  of  the  stomach  and  duodenum  was  found  swollen 
and  loose,  and  in  some  places  entirely  destroyed,  and  at  one  spot  per- 
foration had  taken  place,  due  to  the  corrosive  action  of  the  poison. 
There  were  also  found  hypereemia  of  the  brain  and  its  membranes, 
beginning  fatty  degeneration  of  the  liver,  commencing  icterus,  hyper- 
semia  of  the  kidneys,  suppurative  pyelitis,  and  a  softened  condition 
of  the  spleen. 

Chemical  Properties. 

General  Chemical  ISTature. — Acetate  of  lead,  as  usually 
found  in  the  shops,  is  in  the  form  of  white  crystalline  masses,  which 
have  a  density  of  about  2.6,  a  slight  vinegar-like  odor,  and  a  sweet- 
ish, astringent  taste.  In  its  crystalline  state  this  salt  consists  of  one 
atom  of  lead,  two  molecules  of  acetic  acid,  with  three  of  water, 
Pb2C2ll302 ;  3Aq ;  it  crystallizes  in  four-sided  prisms.  When  the 
crystals  are  exposed  to  dry  air  they  slightly  effloresce,  and  after  a 
time  become  partially  converted  into  lead  carbonate,  from  the  absorp- 
tion of  carbonic  acid  from  the  atmosphere.    When  moderately  heated, 


SPECIAL   CHEMICAL   PROPERTIES.  369 

they  fuse  and  give  oil"  tlieir  water  of  erystalHzation ;  at  higher  tem- 
peratures the  salt  undergoes  complete  decomposition,  leaving  a  black 
residue  consisting  of  a  mixture  of  charcoal  and  metallic  lead. 

Solubility.  1.  In  Water. — When  finely  powdered  crystallized 
acetate  of  load  is  agitated  for  a  few  minutes  with  its  own  weight  of 
water,  at  a  temperature  of  15.5°  C.  (60°  F.),  and  the  liquid  quickly 
filtered,  crystals  of  the  salt  immediately  begin  to  separate  from  the 
filtrate;  if  this  mixture  be  allowed  to  evaporate  spontaneously,  it 
leaves  a  crystalline  residue,  indicating  that  the  filtered  fluid  originally 
held  in  solution  one  part  of  the  salt  in  1.62  parts  of  the  liquid. 

When  the  powdered  salt  is  agitated  for  a  few  minutes  with  an 
equal  weight  of  water  at  a  temperature  of  15.5°  C.  (60°  F.),  and 
the  mixture  allowed  to  stand  at  about  the  same  temperature  for 
forty-eight  hours,  and  the  liquid  then  filtered,  the  filtrate  contains 
only  one  part  of  the  salt  in  2.67  parts  of  water. 

From  these  experiments  it  is  obvious  that  the  mere  act  of  agita- 
tion very  much  increases  the  solubility  of  this  salt  in  water.  This 
circumstance  may,  in  part  at  least,  account  for  the  discrepant  state- 
ments of  observers  in  regard  to  the  solubility  of  the  salt. 

2.  In  Alcohol. — When  large  excess  of  the  pulverized  salt  is 
agitated  for  a  few  minutes  with  pure  alcohol  of  97  per  cent.,  and  the 
solution  quickly  filtered,  the  filtrate  contains  one  part  of  the  salt  in 
twenty  parts  of  the  liquid.  But  if,  after  agitating  the  mixture  for 
a  few  minutes,  it  be  allowed  to  stand  quietly  for  twenty-four  hours 
and  the  liquid  then  filtered,  the  filtrate  contains  only  one  part  of  the 
salt  in  about  sixty-five  parts  of  the  menstruum. 

The  more  dilute  the  alcohol,  other  conditions  being  equal,  the 
greater  will  be  the  quantity  of  the  salt  that  it  will  dissolve. 

3.  In  Ether. — Absolute  ether,  under  any  circumstance,  fails  to 
dissolve  an  appreciable  trace  of  the  salt. 

Special  Chemical  Properties. — When  acetate  of  lead,  in  its 
solid  state,  is  moistened  with  a  solution  of  potassium  iodide,  it  assumes 
a  bright  yellow  color,  due  to  the  formation  of  iodide  of  lead.  The 
least  visible  quantity  of  the  salt  will  exhibit  this  reaction.  Thus, 
a  residue  representing  only  1-1 000th  of  a  grain  of  lead  oxide  will 
yield  a  very  satisfactory  bright  yellow  coloration ;  and  even  the 
l-10,000th  of  a  grain,  when  deposited  at  one  point,  will  assume  a 
distinct  yellow  hue.  The  lead  iodide  thus  produced  is  slowly  soluble 
in  large  excess  of  the  reagent. 

24 


370  LEAD. 

If  a  small  portion  of  the  salt  be  introduced  into  a  drop  of  potas- 
sium chromate  solution,  it  also  assumes  a  bright  yellow  color,  lead 
chromate  being  formed.  Crushing  the  crystal  facilitates  the  forma- 
tion of  the  yellow  compound. 

When  gradually  heated  on  a  piece  of  porcelain,  acetate  of  lead 
fuses  to  a  clear  liquid,  boils,  and  then  becomes  reduced  to  a  white, 
anhydrous  mass ;  if  the  heat  be  continued,  the  mass  again  fuses,  then 
becomes  dry  and  charred,  and  slowly  assumes  a  yellowish  or  reddish- 
brown  color.  This  residue  consists  of  a  mixture,  in  variable  propor- 
tions, of  different  oxides  of  lead.  Almost  the  least  visible  crystal 
of  the  salt,  when  thus  treated,  leaves  a  brownish  residue,  apparently 
several  times  greater  than  the  crystal  employed.  The  carbonate  of 
lead,  when  treated  in  this  manner,  does  not  fuse ;  but  it  is  slowly 
decomposed,  with  the  production  of  a  similar  reddish-brown  residue. 

Heated  upon  a  piece  of  charcoal  in  the  inner  blow-pipe  flame, 
acetate  of  lead  fuses,  then  undergoes  decomposition,  with  the  produc- 
tion of  bright,  malleable  globules  of  metallic  lead,  and  the  formation 
of  a  yellow  incrustation  of  oxide  of  lead.  The  carbonate  of  lead, 
under  these  circumstances,  yields  at  first  a  brownish  mass,  which 
soon  furnishes  bright,  metallic  globules. 

When  acetate  of  lead  is  placed  in  a  small  quantity  of  ferric 
chloride  solution,  it  slowly  dissolves  to  a  fine  red  solution  of  ferric 
acetate,  FegGCaHgOg.  If  the  salt  be  heated  in  a  test-tube  with 
concentrated  sulphuric  acid,  it  undergoes  decomposition,  with  the 
evolution  of  pungent  vapors  of  acetic  acid.  When  heated  with  a 
mixture  of  equal  volumes  of  alcohol  and  sulphuric  acid,  it  evolves 
acetic  ether,  readily  recognized  by  its  peculiar  aromatic  odor.  These 
reactions  are  simply  due  to  the  acetic  acid  of  the  lead  salt,  and  are 
common  to  all  acetates. 

Pure  aqueous  solutions  of  lead  acetate  are  colorless,  odorless, 
and  have  a  sweetish,  styptic  taste,  and,  if  not  too  dilute,  a  feebly 
acid  reaction.  When  a  solution  of  this  kind  is  allowed  to  evapo- 
rate spontaneously,  the  salt  is  left  in  the  form  of  white,  crystalline 
needles. 

In  the  following  examinations  in  regard  to  the  behavior  of  re- 
agents with  solutions  of  lead,  the  pure  crystallized  acetate  was  dis- 
solved in  water  very  slightly  acidulated  with  acetic  acid.  The 
fractions  employed  indicate  the  fractional  part  of  a  grain  of  lead 
oxide,  PbO,  or  its  equivalent,  in  solution  in  one  grain  of  the  liquid. 


SULPHURETTED    HYDROGEN   TEST.  371 

Except  wlioii  otiierwise  iiulicated,  tlio  results  refer  to  the  beliavior 
of  one  grain  of  the  solution.  One  part  of  lead  oxide  represents 
1.696  parts  of  crystallized  acetate  of  lead. 

1.  Sulphuretted  Hydrogen. 

This  reagent,  either  in  its  gaseous  state  or  in  the  form  of  an 
alkaline  sulphide,  throws  down  from  neidral,  acidulated,  and  alka- 
line solutions  containing  lead  a  black,  amorphous  precipitate  of  lead 
sulphide,  PbS,  which  is  insoluble  in  the  caustic  alkalies  and  in  the 
diluted  uiineral  acids.  Hot  concentrated  hydrochloric  acid  dissolves 
the  precipitate,  with  the  evolution  of  sulphuretted  hydrogen  and 
the  formation  of  lead  chloride,  which,  unless  the  quantity  be  very 
minute,  separates,  as  the  liquid  cools,  in  the  form  of  beautiful  crys- 
talline plates. 

The  precipitate  is  readily  decomposed  by  hot  nitric  acid,  with 
the  formation  of  lead  nitrate  and  the  separation  of  free  sulphur ;  if 
the  acid  be  concentrated  and  the  heat  continued,  the  separated  sul- 
phur becomes  oxidized  into  sulphuric  acid,  which,  displacing  the 
nitric  acid,  unites  with  the  lead,  forming  lead  sulphate.  The  sul- 
phate of  lead  thus  formed  generally  separates .  in  the  form  of  a 
white,  granular  powder,  but  sometimes  in  the  form  of  small,  bril- 
liant crystalline  plates ;  if,  however,  the  quantity  of  the  lead  salt 
produced  be  only  small,  it  may  remain  in  solution  in  any  excess  of 
nitric  acid  present. 

In  examining  the  limit  of  the  reaction  of  this  reagent,  a  slow 
stream  of  the  washed  sulphuretted  gas  was  passed  into  ten  grains  of 
the  lead  solution,  contained  in  a  small  test-tube. 

1.  1-lOOth    solution    (=  -j^Qth   grain   PbO)   yields   an    immediate, 

copious,  black  deposit.  When  the  precipitate  is  dissolved  in 
the  mixture,  by  excess  of  hydrochloric  acid,  it  yields  a  white 
precipitate  of  crystalline  needles  of  lead  chloride. 

2.  1-lOOOth   solution    yields   an    immediate   precipitate.     When  a 

solution  of  this  strength  is  exposed  to  the  vapor  of  sulphu- 
retted hydrogen,  its  surface  becomes  covered  with  a  black 
pellicle  of  lead  sulphide. 

3.  l-10,000th  solution  :  the  first  bubble  of  the  reagent  produces  a 

deep  brown  coloration ;  and  a  few  bubbles  produce  a  deep  brown 
turbidity.     After  saturating  the  solution  with  the  reagent,  and 


372  LEAD. 

allowing  it  to  stand  an  hour,  a  very  satisfactory  black  deposit 
separates. 

4.  l-50,000th  solution :  after  a  few  moments  the  liquid  assumes  a 

distinct  brown  color,  and  very  soon  presents  a  brown  turbidity ; 
after  a  few  hours  distinct  brownish  flakes  separate. 

5.  l-100,000th  solution :  after  some  minutes  the  liquid  assumes  a 

distinct  brownish  tint,  and  soon  afterward  becomes  turbid :  after 
some  few  hours  the  brownish  color  deepens,  but  no  deposit 
separates. 

6.  l-250,000th  solution :  after  several  minutes  the  liquid  assumes 

a  just  perceptible  cloudiness,  with  a  faint  brownish  tint,  which 
is  only  distinctly  observed  when  compared  with  a  clear  solution, 
and  best  seen  by  looking  through  the  liquid  from  the  top. 
The  formation  of  the  precipitate  from  very  dilute  solutions  is 
much  facilitated  by  heating  the  mixture.     The  delicacy  of  the  reac- 
tion of  this  test  has  been  variously  stated.     Thus,  Pfaff  placed  the 
limit  of  the  brown  coloration  at  one  part  of  lead  oxide,  in  the  form 
of  nitrate,  in  100,000  parts  of  liquid ;  Lassaigne,  at  200,000  parts ; 
and  Harting,  at  350,000  parts.     As,  however,  neither  of  these  ob- 
servers states  the  amount  of  the  solution  operated  upon,  these  dis- 
crepancies are  readily  explained. 

Fallacies. — The  production  of  a  black  precipitate  by  this  reagent 
is  common  to  solutions  of  several  other  metals  besides  lead.  The  true 
nature  of  the  lead  precipitate  may  be  established  by  dissolving  it,  by 
the  aid  of  heat,  in  diluted  nitric  acid  containing  just  suflScient  of  the 
acid  to  effect  decomposition,  and  then  testing  the  solution  with  either 
potassium  iodide  or  potassium  chromate,  or  with  diluted  sulphuric 
acid;  or,  after  filtration,  the  nitric  acid  solution  may  be  evaporated 
to  dryness,  and  the  residue  examined  by  any  of  the  tests  already 
mentioned  for  salts  of  the  metal  when  in  the  solid  state. 

When  strongly  heated  in  a  reduction-tube,  lead  sulphide  is  con- 
verted into  a  hard,  brittle  mass,  but  fails  to  yield  a  sublimate. 

2.  Sulphuric  Acid. 

This  acid  and  its  soluble  salts  throw  down  from  solutions  of  salts 
of  lead  a  heavy,  white  precipitate  of  lead  sulphate,  PbSOi,  which  is 
soluble  in  large  excess  of  the  fixed  alkalies,  and  in  some  of  the  salts 
of  ammonium,  but  very  sparingly  soluble  in  diluted  nitric  and  hy- 
drochloric acids.     Strong  nitric  acid  dissolves  it  in  limited  quantity 


UYDKOCIILOKIC    ACID    TKST.  373 

to  a  clear  solution.  Concentrated  hydrochloric  acid  dissolves  it  rather 
readily,  especially  upon  the  application  of  heat,  yielding  crystals  of 
lead  chloride  as  the  mixture  cools. 

From  very  dilute  solutions  of  salts  of  lead  the  precipitated  sul- 
phate does  not  separate  until  after  some  time:  it  then  deposits  in  the 
form  of  small  granules.  Solutions  of  the  alkaline  carbonates,  nor- 
mal and  acid,  convert  lead  sulphate,  even  at  ordinary  temperatures, 
into  lead  carbonate;  solutions  of  normal  alkaline  carbonates,  but  not 
those  of  the  acid  carbonates,  dissolve  some  of  the  lead  compound  in 
this  process  (H.  Rose).  From  an  alkaline  solution  of  lead  sulphate 
the  metal  is  precipitated  by  sulphuretted  hydrogen  as  lead  sulphide. 

1.  -j-g-g-  grain  of  lead  oxide,  or  its  equivalent,  in  one  grain  of  liquid, 

yields  with  a  drop  of  dilute  sulphuric  acid  a  copious  precipi- 
tate, which  partly  consists  of  crystalline  needles.  If  the  drop 
of  reagent  be  allowed  to  flow  slowly  into  the  lead  solution,  the 
precipitate  generally  consists  of  a  mass  of  crystalline  needles, 
Plate  Y.,  fig.  3. 

2.  Yxroir  grain  yields  a  good   precipitate,  consisting  principally  of 

needles  and  granules. 

3.  5-^0-j}-  grain :  an  immediate  granular  precipitate,  and   in  a  little 

time  a  quite  fair  deposit. 

4.  ru",V(nr  grain :  after  a  few  moments  a  cloudiness  appears,  and  in 

a  little  time  there  is  a  very  satisfactory  granular  deposit. 

5.  2U.W(r  grain  yields  after  a  few  moments  a  slight  cloudiness,  and 

after  a  little  time  a  satisfactory  granular  precipitate. 

If  potassium  sulphate  be  employed  as  the  reagent,  it  produces 
the  same  results  as  the  above. 

Free  sulphuric  acid,  as  well  as  soluble  sulphates,  also  produces 
white  precipitates  in  solutions  of  barium  and  strontium  salts.  The 
lead  sulphate,  however,  is  distinguished  from  that  of  either  of  these 
metals,  in  that  when  moistened  with  ammonium  sulphide  it  is  turned 
black,  due  to  the  formation  of  lead  sulphide.  When  lead  sulphate 
is  intimately  mixed  with  sodium  carbonate  and  heated  before  the 
blow-pipe  flame,  on  a  charcoal  support,  it  yields  globules  of  metallic 
lead, 

3.  Hydrochloric  Acid. 

Hydrochloric  acid  and  its  soluble  salts  occasion  in  somewhat 
strong  solutions  of  lead  salts  a  white  precipitate  of  lead  chloride, 


374  LEAD. 

PbCl2,  which  is  less  soluble  in  diluted  hydrochloric  and  nitric  acids 
than  in  pure  water.  When  excess  of  lead  chloride  is  digested,  at  the 
ordinary  temperature,  with  pure  water  for  forty-eight  hours,  one  part 
of  the  salt  dissolves  in  110  parts  of  the  liquid  :  it  is  much  more 
soluble  in  hot  water.  It  is  readily  soluble  in  concentrated  hydro- 
chloric acid.  Chloride  of  lead  bears  a  strong  heat  without  decom- 
position ;  but  at  higher  temperatures,  with  a  free  supply  of  air,  it  is 
partially  decomposed,  with  the  evolution  of  chlorine,  and  leaves  a 
residue  consisting  of  a  mixture  of  oxide  and  chloride  of  lead. 

1.  yl-Q-  grain  of  lead  oxide,  in  one  grain  of  water,  yields,  with  free 

hydrochloric  acid,  a  copious,  white  crystalline  precipitate,  Plate 
v.,  fig.  4. 

2.  -g-^  grain :  in  a  very  little  time  a  very  fair  deposit  of  granules 

and  crystalline  needles. 

3.  YWo^  grain  yields  after  some  minutes  a  quite  satisfactory  deposit 

of  granules,  needles,  and  prisms. 

The  results  under  2  and  3  are  obtained  only  when  excess  of 
hydrochloric  acid  is  employed. 

This  reagent,  as  well  as  soluble  chlorides,  also  produces  white 
precipitates  in  solutions  of  silver  and  of  mercurous  salts.  The 
chlorides  of  silver  and  mercury,  however,  are  always  thrown  down 
in  the  amorphous  form.  The  precipitated  lead  chloride  is  insolu- 
ble, and  unchanged  in  color,  by  caustic  ammonia ;  whereas  the  silver 
precipitate  is  readily  soluble  in  that  alkali,  whilst  the  mercury  com- 
pound is  turned  black.  The  action  of  ammonia,  therefore,  readily 
serves  to  distinguish  between  the  chlorides  of  these  three  metals. 
Moreover,  the  lead  chloride  is  readily  soluble,  especially  by  the  aid  of 
heat,  in  large  excess  of  water,  whereas,  on  the  other  hand,  the  silver 
chloride  and  mercurous  chloride  are  wholly  insoluble  in  this  liquid. 

4.  Potassium  Iodide. 

This  reagent  produces  in  solutions  of  salts  of  lead  a  bright 
yellow  precipitate  of  lead  iodide,  Pblg,  which  is  readily  soluble  to  a 
clear  solution  in  potassium  hydrate,  but  almost  wholly  insoluble  even 
in  very  large  excess  of  the  precipitant;  under  the  action  of  ammo- 
nia it  slowly  assumes  a  white  color.  It  dissolves  to  a  clear  solution 
in  strong  hydrochloric  acid ;  nitric  acid  dissolves  it  to  lead  nitrate. 
Heated  before  the  blow-pipe,  on  charcoal,  it  turns  reddish-yellow, 
then  becomes  brownish,  and  finally  volatilizes. 


POTASSIUM   CH  ROM  ATE  TEST.  375 

Todido  of  lead  is  hut  sparingly  soluble  in  cold  water,  but  at  the 
boilini;-  torn pcnit lire  it  dissolves  more  freely,  and  separates,  as  tlie 
liquid  cools,  in  beautiful,  six-sided  laiuinfe.  We  have  found  that 
when  excess  of  the  well-washed  salt  is  digested  in  pure  water,  with 
frequent  agitation  for  twenty-four  hours,  at  a  temperature  ranging 
from  15°  to  21°  C.  (G0°  to  70°  F.),  one  part  dissolves  in  1528  parts 
of  the  fluid.  It  is,  however,  much  less  soluble  in  a  dilute  solution 
of  potassium  iodide.  This  reagent,  therefore,  produces  a  copious 
precipitate  from  a  pure  saturated  aqueous  solution  of  lead  iodide ; 
even  in  the  preseuce  of  slight  excess  of  the  reagent  a  precipitate  will 
form  when  the  lead  iodide  does  not  form  more  than  the  1-1 0,000th 
part  by  weight  of  the  solution.  The  precipitate  from  a  1-lOOOth 
solution  of  lead  oxide  does  not  usually  entirely  dissolve  by  heating 
the  mixture  to  the  boiling  temperature. 

1.  y-J-jj  grain  of  lead  oxide  yields  a  copious,  bright  yellow  precipitate, 

which  is  usually  partly  granular  and  crystalline. 

2.  YU^  grain  yields  a  very  good  deposit. 

3.  2tW  gr^in  yields  a  quite  good  precipitate,  which  readily  dissolves 

by  heating  tlie  mixture  to  the  boiling  temperature,  and  again 
separates,  as  the  liquid  cools,  in  brilliant,  golden-yellow,  six- 
sided  plates,  Plate  V.,  fig.  5. 

4.  5-0V0  grain  :  a  very  fair  deposit. 

5.  YcT.ToTr  grain  yields  an  immediate  yellow  precipitate,  which  soon 

becomes  a  fair  deposit. 

6.  Y^.uim  grain  yields,  with  a  very  small  quantity  of  the  reagent, 

after  a  little  time,  a  quite  satisfactory  deposit  of  granules  and 
small  plates. 
The  production,  by  this  reagent,  of  a  yellow  precipitate,  which  is 
soluble  in  boiling  water,  and  separates  as  the  mixture  cools,  in  the 
form  of  six-sided  plates,  is  characteristic  of  lead. 

5.  Potassium  Chr ornate. 

Potassium  chromate  and  the  dichromate  throw  down  from  so- 
lutions of  salts  of  lead  a  bright  yellow,  amorphous  precipitate  of 
lead  chromate,  PbCiO^,  which  is  insoluble  in  acetic  acid,  and  only 
sparingly  soluble  in  diluted  nitric  acid,  but  readily  soluble  in  potas- 
sium hydrate.  Hydrochloric  acid  slowly  changes  it  to  white  lead 
chloride;  it  is  blackened  by  ammonium  sulphide. 
1.  j^  grain  of  lead  oxide  yields  a  copious  precipitate. 


376  LEAD. 

2.  YWoT  g'^aiii  •  ^  very  good  deposit. 

3.  Yo'.'UTo'  g'^^iii  yields  a  quite  good,  greenish-yellow  precipitate. 

4.  -^^.-g-oo-  grain  yields  an  immediate  cloudiness,  and  in  a  few  minutes 

a  very  satisfactory  greenish  deposit. 

5.  YWohro  gi"ain  yields  after  a  little  time  a  greenish  turbidity. 

The  formation  of  the  deposit  from  dilute  solutions  is  facilitated 
by  heating  the  mixture. 

Potassium  chromate  produces  in  dilute  neutral  solutions  of  salts 
of  copper  a  yellowish  precipitate,  which  after  a  time  assumes  a 
reddish-brown  color,  and  which,  unlike  the  lead  chromate,  is  readily 
soluble  in  acetic  acid.  The  precipitate  from  somewhat  strong  solu- 
tions of  copper  has  at  once  a  reddish-brown  color.  Potassium  di- 
chromate  produces  no  precipitate  from  even  concentrated  solutions 
of  salts  of  copper. 

6.  Potassium  Hydrate  and  Ammonia. 

The  caustic  alkalies  produce  in  solutions  of  salts  of  lead  a  white 
precipitate,  consisting  chiefly  of  the  hydrated  oxide  of  lead,  which  is 
readily  soluble  in  large  excess  of  the  fixed  alkalies,  insoluble  in  am- 
monia, and  but  sparingly  soluble  in  ammonium  nitrate.  The  precipi- 
tate is  readily  soluble  in  nitric  acid,  and  is  changed  to  lead  chloride 
by  hydrochloric  acid.  Upon  the  addition  of  sulphuretted  hydrogen 
or  ammonium  sulphide,  the  precipitate  is  changed  to  black  sulphide 
of  lead. 

From  solutions  of  acetate  of  lead  ammonia  causes  only  a  partial 
precipitate,  due  to  the  formation  of  triplumbic  acetate  (tribasic  acetate 
of  lead),  2PbO ;  Pb2C2H302,  which  remains  in  solution. 

1.  y-J-g-  grain  of  lead  oxide  yields  with  either  of  the  fixed  alkalies 

a  copious,  white,  amorphous  deposit. 

2.  Y^^  grain :  a  very  good  precipitate,  which  is  readily  soluble  in 

excess  of  the  precipitant. 

3.  xo.Too"  grain  yields  with  a  very  small  quantity  of  the  reagent  a 

very  satisfactory  deposit. 
These  reagents  also  produce  white  precipitates  with  solutions  of 
several  other  metals,  which  in  some  instances,  as  with  bismuth  and 
tin,  are,  like  the  lead  deposit,  blackened  by  ammonium  sulphide. 
When,  however,  the  dried  lead  precipitate  is  heated  on  charcoal 
before  the  reducing  flame  of  the  blow-pipe,  it  leaves  malleable 
metallic  globules,  which  are  characteristic  of  this  metal. 


REACTIONS    WITH    REAGENTS.  377 


7.  Alkaline  Carbonates. 

The  allcaline  carbonates  occasion  in  solutions  of  salts  of  lead  a 
white  amorphous  precipitate  of  lead  carbonate,  together  witli  more 
or  less  hydrated  oxide  of  the  metal.  The  precipitate  is  almost 
wholly  insoluble  in  excess  of  the  precipitant,  but  readily  soluble  in 
nitric  and  acetic  acids,  and  is  changed  to  lead  chloride  by  hydro- 
chloric acid ;  it  is  also  readily  soluble  in  large  excess  of  the  fixed 
caustic  alkalies. 

1.  Yffy-  grain  of  lead  oxide,  in  one  grain  of  water,  yields  a  copious 

precipitate. 

2.  YoVu"  gi'ai^  •  a  very  good  deposit. 

3.  -j-jj.^-g-jj  grain  :  a  very  satisfactory  precipitate. 

4.  ■Bu-.-g-g-jr  grain  yields  within  a  few  minutes  a  quite  distinct  cloudi- 

ness. 
These  reagents  also  produce  white  precipitates  in  solutions  of 
many  other  metals.     But  from  all  these  precipitates  the  lead  com- 
pound is  readily  distinguished  by  its  behavior  before  the  blow-pipe 
flame. 

8.  Ammonium  Oxalate. 

This  reagent  produces  in  neutral  solutions  of  salts  of  lead  a 
white  precipitate  of  lead  oxalate,  which  soon  becomes  crystalline. 
The  precipitate  is  readily  soluble  in  nitric  acid,  but  insoluble  in 
acetic  acid,  and  blackened  by  ammonium  sulphide. 

1.  Y^  grain  of  lead  oxide  yields  a  copious  precipitate,  which  soon 

changes  to  a  mass  of  long  crystalline  needles. 

2.  YoVo"  gr^^n  yields  a  very  good  deposit,  which  soon  changes  to 

granules  and  groups  of  needles. 

3.  T-o-Voir  grain  yields  an  immediate  cloudiness,  and  after  a  little 

time  a  quite  distinct  deposit. 

4.  -g-g^.^-ij-g-  grain  yields  after  some  minutes  a  quite  satisfactory  tur- 

bidity. 
When  lead  oxalate  is  heated  before  the  blow-pipe  on  a  charcoal 
support,  it  yields  globules  of  metallic  lead. 

9.  Zinc  Test. 

When  a  drop  of  a  solution  of  acetate  of  lead  is  placed  in  a 
watch-glass,  and  a  fragment  of  bright  zinc  added,  the  lead  com- 


378  LEAD. 

pound  is  slowly  decomposed,  with  the  deposition  of  metallic  lead 
upon  the  zinc,  in  the  form  of  a  brush-like,  crystalline  deposit.  If 
the  lead  solution  be  placed  upon  a  piece  of  bright  copper  and  the 
metal  touched  through  the  drop  with  a  needle  of  zinc,  the  lead 
deposits  partly  on  the  zinc  and  partly  on  the  copper,  as  a  strongly 
adhering,  gray  deposit,  over  the  space  occupied  by  the  drop. 

1.  YoT  graiii  of  lead  oxide,  when  placed  in  a  watch-glass  and  treated 

as  just  stated,  yields  a  quite  large,  brush-like  deposit. 

2.  YoTo   grain  :  the  zinc  immediately  darkens,  and  in  a  little  time 

receives  a  quite  satisfactory  deposit. 
A  solution  of  tin  yields  with  a  fragment  of  zinc  a  brush-like 
deposit  of  metallic  tin,  which  sometimes  very  closely  resembles  that 
produced  under  similar  conditions  by  lead. 

Potassium  Jerroeyanide  produces  in  solutions  of  salts  of  lead 
a  white  amorphous  precipitate  of  ferrocyanide  of  lead,  PbaFeCyg, 
which  is  slowly  soluble  in  large  excess  of  nitric  acid,  and  changed 
to  lead  chloride  by  hydrochloric  acid.  One  grain  of  a  1-1 000th 
solution  of  lead  oxide  yields  with  this  reagent  a  quite  good  precipi- 
tate; and  the  same  quantity  of  a  l-10,000th  solution  gives  after  a 
little  time  a  quite  satisfactory  deposit. 

Potassium  ferricyanide  throws  down  from  solutions  of  acetate 
of  lead  a  dirty-yellow  precipitate,  which  is  soluble  in  nitric  acid, 
decomposed  by  hydrochloric  acid,  and  blackened  by  ammonium  sul- 
phide. With  one  grain  of  a  1-1 000th  solution  of  lead  oxide  the 
reagent  produces  a  quite  good  amorphous  deposit;  one  grain  of  a 
1— 10,000th  solution  yields  after  a  few  minutes  a  quite  satisfactory 
granular  precipitate. 

Both  these  reagents  produce  some^vhat  similar  precipitates  in 
solutions  of  several  other  metals. 

Sepaeatiox  from  Orgaxic  Mixtures. 

Suspected  Solutioivs. — Various  kinds  of  animal  and  vegetable 
substances  more  or  less  decompose  and  precipitate  acetate  of  lead 
when  in  solution ;  but  most  of  these  precipitates  are  readily  soluble 
in  diluted  nitric  acid.  When  a  mixture  of  this  kind  is  presented 
for  examination,  it  should  be  acidulated  with  nitric  acid  and  heated 
for  some  time,  then  allowed  to  cool,  the  liquid  filtered,  and  the 
solids  upon  the  filter  washed,  the  washings  being  collected  with  the 


SEPARATION    FUoNf    OIUiANK'    NflXTIIHI-X.  P>7^ 

orifriiml  filtrato,  and  tlu;  solids  reservotl.  TIk-  filtrate,  after  coiux'n- 
tration  it"  ncocssarv,  is  tiion  saturated  willi  siilpliiirctted  liy<lrogen 
giu^,  and  the  mixture  allowed  to  stan<l  it)  a  moderately  warm  |>laee 
for  some  time;  any  |)reeipitate  tlms  pioduced  is  colieeted  on  a  small 
filter,  washed,  and,  while  still  moist,  washed  from  the  filter  into  a 
test-tnhe  or  any  convenient  vessel,  by  means  of  a  jet  of  water  from 
a  wash-bottle. 

When  the  j)recii)itate  lias  completely  subsided,  most  of  the  super- 
natant fluid  is  decanted,  and  the  solid  residue  dissolved,  by  the  aid 
of  a  gentle  heat,  in  the  least  possible  quantity  of  nitric  acid,  added 
drop  by  drop.  By  this  means  any  lead  sulphide  present  will  be 
converted  into  lead  nitrate,  while  the  sulphur  set  free  will  remain 
unoxidized.  The  mixture  is  now  diluted  somewhat  with  pure  water, 
the  liquid  filtered,  and  a  portion  of  the  filtrate  tested  with  a  solu- 
tion of  potassium  chromate.  Other  portions  of  the  filtrate  may  be 
examined  by  any  of  the  other  tests  already  pointed  out. 

The  sulphide  of  lead  precipitated  from  the  1-lOOOth  of  a  grain 
of  lead  oxide,  when  diffused  in  ten  grains  of  water  and  heated  with 
one  drop  of  nitric  acid,  yields  a  clear  solution,  which  gives  with 
reagents  about  the  same  reactions  as  a  1-1 0,000th  solution  of  lead 
oxide.  If  large  excess  of  nitric  acid  has  been  used  for  dissolving 
the  lead  sulphide,  the  filtered  liquid  should  be  carefully  neutralized 
by  pure  potassium  hydrate  before  the  application  of  any  of  the  tests. 

It  would  rarely,  if  ever,  happen  with  organic  mixtures  of  this 
kind  containing  lead  that  the  metal  would  entirely  escape  solution 
in  diluted  nitric  acid.  If,  however,  there  has  been  a  failure  to  detect 
the  metal  by  the  above  method,  the  solids  obtained  by  filtration 
from  the  original  mixture  may  be  boiled  for  some  time  with  water 
containing  about  one-sixth  of  its  volume  of  nitric  acid,  the  solution 
filtered,  the  filtrate  evaporated  to  dryness,  and  the  residue  inciner- 
ated. This  residue  is  treated  with  a  little  nitric  acid,  the  solution 
diluted  with  a  small  quantity  of  water,  then  filtered,  and  the  filtrate 
neutralized  and  tested  in  the  ordinary  manner. 

Contents  of  the  Stomach. — These,  after  the  addition  of  water  if 
necessary,  may  be  acidulated  with  nitric  acid,  and  examined  in  the 
manner  just  described  for  suspected  solutions. 

If  an  alkali  sulphate  had  been  administered  as  an  antidote,  the 
poison  may  be  in  the  form  of  insoluble  lead  sulphate.  Under  these 
circumstances,  the  contents  of  the  stomach  should  be  carefully  exam- 


380  LEAD. 

ined,  and  any  white  powder  found  collected  and  washed,  then  boiled 
with  a  strong  solution  of  pure  caustic  potash,  and  the  lead  precipi- 
tated by  sulphuretted  hydrogen.  Or,  any  lead  sulphate  obtained 
may  be  placed  in  a  wide  test-tube  and  agitated  occasionally  for  sev- 
eral hours  with  a  strong  solution  of  acid  sodium  carbonate,  the  clear 
liquid  decanted,  and  the  operation  repeated  with  a  fresh  portion  of 
the  sodium  solution.  By  this  means  the  lead  sulphate  will  be  con- 
verted into  insoluble  lead  carbonate.  This  is  washed,  then  dissolved 
in  a  little  acetic  acid  or  in  very  dilute  nitric  acid,  and  the  solution 
tested. 

According  to  the  observations  of  Orfila,  in  acute  poisoning  by 
the  salts  of  lead,  the  villous  coat  of  the  stomach  frequently  presents 
numerous  white  points  which  contain  lead,  and  which  are  blackened 
by  sulphuretted  hydrogen. 

From  the  Tissues. — The  solid  organ,  such  as  a  portion  of  the 
liver,  is  cut  into  small  pieces  and  boiled  in  a  porcelain  dish  with 
nitric  acid,  diluted  with  about  four  parts  of  water,  until  the  mixture 
becomes  homogeneous.  AYhen  the  mixture  has  cooled,  the  liquid 
is  filtered,  the  filtrate  evaporated  to  dryness,  the  residue  moistened 
with  nitric  acid,  again  evaporated  to  dryness,  and  the  heat  continued 
until  all  vapors  cease  to  be  evolved  and  the  residue  becomes  a  car- 
bonaceous mass.  The  mass  thus  obtained  is  pulverized  and  boiled 
with  a  small  quantity  of  strong  nitric  acid,  the  mixture  diluted  with 
water,  the  solution  filtered,  the  filtrate  evaporated  to  dryness,  and  the 
residue  dissolved  in  a  small  quantity  of  water  slightly  acidulated 
with  nitric  acid.  This  solution,  after  filtration  if  necessary,  is  satu- 
rated with  sulphuretted  hydrogen  gas,  and  allowed  to  stand  until 
the  precipitate  has  completely  subsided.  Any  lead  sulphide  thus 
deposited  is  collected  on  a  small  filter,  washed,  then  suspended  in 
a  small  quantity  of  water  and  dissolved,  by  the  aid  of  heat,  in  the 
least  possible  quantity  of  nitric  acid,  and  the  solution  tested  in  the 
usual  manner. 

If  the  quantity  of  lead  sulphide  precipitated  by  the  sulphuretted 
gas  is  too  minute  to  be  separated  from  the  filter,  the  filter,  or  that 
portion  of  it  containing  the  deposit,  may  be  heated  with  sufficient 
dilute  nitric  acid  to  dissolve  the  precipitate ;  the  solution  is  then 
filtered,  neutralized,  and  tested. 

From  the  observations  of  several  experimentalists,  it  appears  that 
absorbed  lead  is  very  slowly  eliminated  from  the  system.     Orfila 


QUANTITATIVE   ANALYSIS.  381 

States  {Toxicohgie,  i.  858)  that  wlien  dogs  were  given  alwut  oight 
grains  of  acetate  of  lead  daily  for  one  month,  the  metal  was  found 
in  the  liver  and  brain  of  the  animals  when  killed  ono  hundred  and 
four  davs  after  thoy  had  ceased  to  take  the  poison.  According  to 
this  observer,  tiie  metal  is  eliminated  from  the  body  principally  with 

the  urine. 

From  the  C/rmf?.— Fifteen  or  twenty  ounces  of  the  urine,  acidu- 
lated with  nitric  acid,  may  be  evaporated  to  dryness,  the  residue 
carbonized  by  nitric  acid,  and  the  carbonaceous  mass  treated  in  the 
manner  just  described  for  the  separation  of  the  metal  from  the  tissues. 
By  Ibllowing  this  method  we  detected  the  metal  in  notable  quantity 
in  the  urine  almost  daily  for  about  two  weeks,  in  two  instances  of 
severe  chronic  lead  poisoning  resulting  from  the  use  of  water  col- 
lected in  a  leaden  cistern.  Of  eight  persons  who  used  this  water, 
only  two  were  affected  by  it,  and  these  the  elder  members  of  the 

family. 

Kletzinsky  proposes,  after  rendering  the  urine  alkaline  by  potas- 
sium hydrate,  to  add  about  two  per  cent,  of  its  weight  of  potassium 
nitrate  and  evaporate  to  dryness.  The  residue  is  then  exposed  to  a 
dull  red  heat,  whereby  the  whole  of  the  organic  matter  is  destroyed. 
The  cooled  mass  is  powdered  and  boiled  for  some  time  with  a  half- 
saturated  solution  of  neutral  ammonium  tartrate,  to  which  some 
caustic  ammonia  has  been  added,  the  solution  filtered,  the  filtrate 
acidulated  with  hydrochloric  acid,  and  then  precipitated  by  sulphu- 
retted hydrogen.  The  precipitate  is  allowed  twenty-four  hours  to 
subside,  then  washed,  redissolved  in  warm  dilute  nitric  acid,  and 
the  solution  filtered,  neutralized,  and  tested  in  the  usual  manner. 
(Thudichum,  On  the  Urine,  406.) 

Quantitative  Analysis.— Lead  may  be  very  accurately  esti- 
mated in  the  form  of  sulphide  of  the  metal.  The  solution,  very 
slightly  acidulated  with  nitric  acid,  is  treated  with  a  slow  stream  of 
washed  sulphuretted  hydrogen  gas  as  long  as  a  precipitate  is  pro- 
duced, and  the  mixture  then  allowed  to  stand  in  a  moderately  warm 
place  until  the  precipitate  has  completely  deposited.  The  precipitate 
is  collected  on  a  filter  of  known  weight,  washed,  thoroughly  dried  on 
a  water-bath,  and  weighed.  One  hundred  parts  by  weight  of  the 
dried  sulphide  correspond  to  86.19  parts  of  metallic  lead,  or  93.33 
of  lead  oxide,  or  158.37  of  pure  crystallized  acetate  of  lead. 


382  COPPER. 

When  the  lead  exists  in  the  form  of  sulphate,  this  may  be  washed 
with  water  containing  a  little  alcohol,  dried  at  100°  C.  (212°  F.),  and 
weighed.  One  hundred  parts  by  weight  of  the  dried  sulphate  cor- 
respond to  one  hundred  and  twenty-five  parts  of  crystallized  acetate 
of  lead. 

Section  II. — Copper. 

History  and  Chemical  Nature. — Copper  is  represented  by  the  sym- 
bol Cu;  its  atomic  weight  is  63.4,  and  its  specific  gravity  8.95. 
This  metal  is  frequently  found  in  its  uncombined  state  in  nature ;  its 
most  common  ore  is  copper  pyrites,  which  consists  of  a  mixture  of 
the  sulphides  of  copper  and  iron.  According  to  VValchner,  copper 
is  as  widely  distributed  in  nature  as  iron.  In  some  mineral  waters 
it  is  said  to  exist  to  the  extent  of  half  a  grain  to  the  gallon  of  water. 
It  is  also  found  in  sea-water  and  in  sea-weeds.  Sarzeau  states  that 
he  found  it  in  minute  quantity  in  various  vegetable  substances,  such 
as  coflTee,  sugar,  wheat,  and  flour ;  and  minute  traces  of  it  have  been 
found  in  the  blood  and  various  organs  of  the  healthy  human  body. 
In  fourteen  human  bodies  examined  by  Dr.  G.  Bergeron,  the  metal 
was  found  in  the  liver  in  each  case,  but  in  no  instance  did  the 
amount  exceed  about  one  milligramme  (l-65th  grain)  in  the  entire 
liver.  [Jour,  de  Chim.  Med.,  Nov.  1874,  503.)  In  the  ash  obtained 
from  a  million  parts  of  grain  and  of  flour.  Dr.  Van  den  Berghe 
found  from  eight  to  eleven  parts  of  copper.  (Chem.  Zeit.,  March, 
1882,  223.) 

Copper,  in  its  uncombined  state,  is  a  rather  hard,  quite  tough, 
ductile  metal,  of  a  peculiar  red  color,  and  a  somewhat  granular  frac- 
ture ;  its  fusing  point,  according  to  Daniell,  is  about  1091°  C.  (2000° 
F.).  When  exposed  to  moist  air,  it  slowly  absorbs  oxygen  and  car- 
bonic acid,  with  the  formation  of  a  green  coating  of  hydrated  oxy- 
carbonate  of  copper,  CuOjCuCOgjHaO,  known  also  as  natural  verdi- 
gris. Immersed  in  pure  water,  copper  undergoes  little  or  no  change ; 
but  in  water  containing  common  salt  it  slowly  becomes  covered  with 
a  layer  of  oxychloride  of  the  metal.  In  water  containing  an  organic 
acid,  as  vinegar,  or  when  certain  kinds  of  fatty  matters  are  present, 
the  metal  is  more  readily  acted  upon.  Nitric  acid  rapidly  dissolves 
it,  with  the  evolution  of  nitrogen  dioxide  and  the  formation  of  copper 
nitrate.  Cold  sulphuric  acid  has  no  direct  action  upon  the  metal ; 
but  the  hot  acid  readily  dissolves  it,  with  the  evolution  of  sulphu- 


PHYSIOLOGICAL    EFFECTS.  383 

I'oiis  oxide  gas  (SOj),  to  coj)j)er  sulphate.  Hydrochloric  acid,  even  at 
the  boiliniij  toiu|)C'ratiire,  lulls  to  act  upon  the  metal. 

C'ombinationa, — C<)j)per  readily  unites  with  most  of  the  n<»n- 
metallic  elements.  With  oxygen  it  unites  in  two  proportion.s,  form- 
ing the  monoxide  (C'uO)  and  the  suboxide  (CuoO),  the  former  of 
which  has  a  black,  and  the  latter  a  red,  color.  In  its  hydrated  state 
the  monoxide  has  a  blue  color;  the  color  of  the  hydrated  suboxide 
is  yellow.  The  monoxide  of  copper  readily  unites  with  acids,  form- 
ing salts  known  as  the  cupric  salts,  which  in  their  hydrated  state  have 
either  a  blue  or  a  green  color,  and  several  of  which  are  freely  soluble 
in  water.  The  suboxide  forms  but  few  salts,  and  these  are  quite 
unstable.  The  most  important  compounds  of  copper,  in  regard  to 
their  medico-legal  relations,  are  the  sulphate  and  the  subacetate,  or 
verdigris. 

Sulphate  of  coppe)',  or  blue  vitriol,  in  its  crystallized  state,  has  the 
composition  CuS0j;,5Aq,  its  molecular  weight  being  249.4.  In  this 
state  it  forms  large  blue  crystals,  which  have  a  nauseous  metallic 
taste,  and  a  density  of  2.27.  It  is  soluble  in  between  two  and  three 
times  its  weight  of  water  at  the  ordinary  temperature,  and  in  less 
than  its  own  weight  of  boiling  water :  the  solution  has  a  blue  color, 
and  a  distinctly  acid  reaction.  At  a  temperature  £»f  about  204°  C. 
(400°  F.)  the  salt  becomes  anhydrous  and  crumbles  to  a  nearly  white 
powder ;  at  a  strong  red  heat  it  undergoes  decomposition,  evolving 
free  oxygen  and  sulphurous  oxide,  and  leaving  a  residue  of  copper 
monoxide. 

Verdigris,  as  found  in  the  shops,  is  a  mixture  in  variable  propor- 
tions of  the  lower  acetates  of  copper,  having  either  a  blue  or  a  green 
color,  and  a  disagreeable  acetous  odor.  It  is  usually  met  with  in 
the  form  of  hard,  irregular  masses,  but  sometimes  as  a  fine  powder. 
Under  the  action  of  water  verdigris  is  only  partly  dissolved,  a  green- 
ish residue  of  tribasic  oxyacetate  of  copper  (2CuO ;  CU2C0II3O2)  being 
left.  It  is  completely  soluble  in  water  containing  a  little  free  hvdro- 
chloric  or  nitric  acid.  Sulphuric  acid  readily  decomposes  it,  with  the 
formation  of  copper  sulphate  and  the  elimination  of  acetic  acid. 

Physiological  Effects. — When  swallowed  in  its  metallic  state, 
copper  seems  to  be  entirely  inert,  at  least  so  long  as  it  retains  its 
metallic  form ;  should,  however,  the  metal  become  oxidized  within 
the  alimentary  canal,  it  may  give  rise  to  severe  symptoms.  In  a  case 
quoted  by  Dr.  Beck,  in  w^iich  six  copper  penny-pieces  were  swallowed 


384  COPPER. 

and  retained  in  the  body  for  five  years^  no  inconvenience  was  expe- 
rienced except  the  eifects  of  mechanical  obstruction.  On  the  other 
hand,  a  case  is  related  by  Dr.  Jackson,  of  Boston,  in  which  a  copper 
half-cent  gwallowed  by  a  child  produced  nausea  and  vomiting,  with 
other  symptoms  of  copper  poisoning. 

The  compounds  of  copper,  when  taken  in  large  doses  or  in  fre- 
quently repeated  small  doses,  are  all  more  or  less  poisonous.  Even 
some  of  the  compounds  that  are  insoluble  in  water  are  capable  of  pro- 
ducing very  active  effects.  The  preparations  of  this  metal  have  been 
rarely  administered  for  criminal  purposes;  but  numerous  instances 
are  recorded  of  accidental  poisoning  by  some  of  them,  resulting  from 
the  use  of  food  prepared  in  copper  vessels. 

Symptoms. — The  usual  effects  produced  by  the  preparations  of 
copper  when  swallowed  in  poisonous  quantity  are  a  coppery  taste  in 
the  mouth,  nausea,  a  sense  of  burning  heat  in  the  mouth  and  throat, 
eructations,  severe  headache,  violent  vomiting,  with  more  or  less 
purging,  and  acute  pain  throughout  the  stomach  and  bowels.  The 
pulse  becomes  small,  frequent,  and  irregular ;  and  there  may  be  great 
dizziness,  difficulty  of  breathing,  great  anxiety,  cold  sweats,  extreme 
thirst,  cramps  in  the  extremities,  scantiness  or  entire  suppression  of 
urine,  and  death  is  sometimes  preceded  by  convulsions  and  insensi- 
bility. Among  the  symptoms  occasionally  present  is  jaundice.  Dr. 
Maschka  observed  this  symptom  in  a  case  in  which  death  ensued  on 
the  third  day,  and  he  attributes  it  to  fatty  degeneration  of  the  liver, 
as  in  arsenic  and  phosphorus  poisoning. 

When  taken  in  frequently  repeated  small  doses,  the  preparations 
of  copper  produce  much  the  same  symptoms  as  those  just  described. 
There  is  loss  of  appetite ;  a  coppery  taste  in  the  mouth  ;  nausea,  with 
frequent  efforts  to  vomit ;  violent  headache ;  irregular  and  frequent . 
pulse ;  hot  skin ;  impaired  respiration ;  great  thirst ;  extreme  debility ; 
sharp,  shooting  pains  in  the  stomach,  with  tension  and  tenderness  of 
the  abdomen  ;  frequent  purging,  the  discharges  being  usually  dark- 
colored  and  their  passage  attended  with  pain ;  and  there  is  more  or 
less  alteration  of  the  color  of  the  skin. 

A  not  unfrequent  cause  of  slow  poisoning  by  copper,  as  already 
intimated,  is  the  use  of  utensils  of  the  metal  for  the  preparation  of 
food.  The  risk  of  contamination  in  these  cases  is  always  much  in- 
creased by  the  free  action  of  the  atmosphere,  and  by  allowing  the  food 
to  cool  and  remain  in  contact  with  the  vessel.     By  employing  bright 


PERIOD    WHK.N    FATA  I..  385 

Vessels,  and  rcmovinjj;  the  food  as  soon  as  prepared,  there  is  little 
danjjer  in  tlie  use  of  the  metal  for  such  purposes. 

An  instance  is  related  in  which  ten  persons  partook  of  sou|)  pre- 
pared in  a  copper  vessel  that  had  not  been  properly  cleaned.  They 
all  speedily  sullbrcd  most  violent  symptoms,  and  five  of  the  j)ersons 
died  IVom  its  ciVects  within  several  hours  after  the  souj)  had  been 
taken.     {Jour,  de  Cliim.  Mhl,  July,  1870,  334.) 

Period  ichcn  Fatal. — The  time  at  which  death  has  taken  j)lnce,  in 
acute  poisoning  by  copper,  has  been  subject  to  considerable  variation. 
In  the  case  of  a  young  lady,  mentioned  by  Dr.  Percival,  death  oc- 
curred on  the  ninth  day.  In  this  case  tiie  poisoning  resulted  from 
the  eating  of  pickles  contaminated  with  copper.  The  symptoms 
were  sharp  pains  in  the  stomach,  an  eruption  over  the  breast,  general 
shooting  pains,  thirst,  a  small,  frequent  pulse,  vomiting,  iiiccough, 
and  purging :  there  were  neither  convulsions  nor  stupor.  In  a  case 
related  by  Pyl,  two  ounces  of  verdigris  proved  fatal  in  three  days 
to  a  woman.  In  another  instance,  quoted  by  Dr.  Christison,  a  lady 
and  her  daughter  were  poisoned  by  sour-krout  which  had  been  kept 
in  a  copper  vessel.  They  were  soon  seized  with  pain  in  the  stomach, 
then  nausea  and  vomiting,  followed  by  purging,  convulsions,  and  in- 
sensibility. The  daughter  died  in  twelve  hours,  and  the  mother  an 
hour  later.  [On  Poisons,  362.)  A  child,  aged  sixteen  months,  swal- 
lowed an  unknown  quantity  of  solid  sulphate  of  copper,  and  died 
from  its  effects  four  hours  afterward.  This  is  perhaps  the  most 
rapidly  fatal  case  yet  recorded. 

Fatal  Quantity. — In  a  case  quoted  by  Dr.  Beck,  one  ounce  of 
sulphate  of  copper,  taken  with  suicidal  intent  by  a  man  aged  forty 
years,  proved  fatal  within  twelve  hours.  {Med.  Jur.,  ii.  667.)  In 
another  instance,  seven  drachms  of  the  same  salt,  with  three  drachms 
of  sulphate  of  iron,  caused  the  death  of  an  adult  in  three  days. 
Dr.  Percival  states  that  the  most  violent  convulsions  he  ever  wit- 
nessed were  produced  in  a  young  woman  by  two  drachms  of  blue 
vitriol :  under  appropriate  treatment  she  recovered.  In  a  case  cited 
by  Dr.  Taylor,  half  an  ounce  of  verdigris  destroyed  the  life  of  a 
woman  in  sixty  hours;  and  in  another,  about  twenty  grains  of  the 
subchloride  of  copper  caused  the  death  of  a  child.  {On  Poisons, 
524.) 

On  the  other  hand,  Dr.  Vergely  reports  a  case  {Jour,  de  Chim. 
Med.,  April,  1873,  152)  in  which  a  w'oman,  aged  thirty-two  years, 

26 


386  cx)PPER. 

drank  a  solution  of  fifteen  grammes  (about  two  hundred  and  thirty- 
two  grains)  of  copper  sulphate,  and  speedily  experienced  violent 
symptoms  of  copper  poisoning;  but  under  active  treatment  she 
entirely  recovered  within  a  few  days.  And  in  a  case  quoted  by 
Dr.  A.  Stills  {3fat.  Med.,  i.  325),  in  which  an  ounce  of  blue  vitriol 
had  been  swallowed  with  suicidal  intent,  complete  recovery  took 
place,  although  the  patient  refused  to  take  an  emetic. 

Treatment. — In  acute  poisoning  by  any  of  the  preparations  of 
copper,  the  vomiting  should  be  encouraged  by  the  free  administration 
of  demulcent  liquids ;  or  the  stomach  may  be  emptied  by  means  of 
the  stomach-pump.  As  a  chemical  antidote,  albumen  in  large  excess 
was  strongly  advised  by  Orfila.  The  white  of  egg  should  be  freely 
given,  and  its  exhibition  followed  by  large  draughts  of  tepid  water. 
An  excess  of  albumen  readily  decomposes  the  soluble  salts  of  copper, 
with  the  formation  of  albuminate  of  copper,  which  is  said  to  be  but 
sparingly  soluble  in  the  juices  of  the  stomach. 

According  to  the  experiments  of  Dr.  Schrader,  of  Gottingen, 
milk  is  equally  efficient  witli  albumen  as  an  antidote.  The  case- 
ate  of  copper  thus  produced  should  be  speedily  removed  from  the 
stomach  by  vomiting.  [Amer.  Jour.  Med.  Sci.,  Oct.  1855,  540.) 
M.  Duval  strongly  advised  the  use  of  sugar ;  but  it  is  very  ques- 
tionable whether  this  substance  can  be  regarded  as  an  antidote :  it 
might,  however,  be  administered  in  connection  with  albumen  or 
milk. 

Among  the  other  substances  that  have  been  proposed  as  anti- 
dotes may  be  mentioned  potassium  ferrocyauide,  iron  filings,  calcined 
magnesia,  and  hydrated  sulphide  of  iron.  The  employment  of  the 
alkaline  sulphides,  and  also  of  vinegar,  would  be  inadmissible. 

Post-mortem  Appeaeaxces. — The  morbid  appearances  in  poi- 
soning by  the  preparations  of  copper  are  usually  confined  to  the 
alimentary  canal.  In  acute  cases,  the  inside  of  the  stomach  and  of 
the  intestines  not  unfrequently  presents  a  bluish  or  greenish  appear- 
ance, due  to  the  presence  of  the  poisonous  compound.  It  should  be 
remembered,  however,  as  first  pointed  out  by  Orfila,  that  a  some- 
what similar  appearance  may  result  from  the  presence  of  altered 
bile.  The  lining  membrane  of  the  stomach  is  usually  inflamed  and 
softened ;  and  in  some  few  instances  it  presented  an  ulcerated,  and 
even  gangrenous,  appearance.  Similar  aj)pearances  have  been  found 
in  the  intestines ;  in  some  few  cases  the  intestines  were  found  per- 


CHEMICAL   PROPERTIES.  387 

forated,  ami  (ln'ir  contents  had   partially  escaped   into  the  cavity  of 
the  abdomen. 

In  the  fatal  case  cited  by  l^r.  Bc(!k,  the  <es(»])ha;i;u.s  was  found  of 
a  livid-red  color,  and  the  stomach  of  a  bluish  hue,  which  could  be 
removed  by  washing;  under  this,  the  mucous  membrane  was  of  a 
deep  red  color.  The  intestinal  tube,  throughout  its  whole  extent, 
was  highly  inflamed.  In  the  case  before  referred  to,  in  which  seven 
drachms  of  sulphate  of  copper,  together  with  three  drachms  of  green 
vitriol,  had  been  taken,  the  mucous  metnbrane  throughout  the  stom- 
ach and  intestines  was  found  in  a  perfectly  healthy  condition. 

Chemical  Properties. 

Ix  THE  Solid  State. — The  general  chemical  nature  and  prop- 
erties of  the  sulphate  and  subacetates  of  copper,  or  verdigris,  have 
already  been  pointed  out.  The  nitrate  of  copper  has  a  beautiful 
blue  color,  and  is  freely  soluble  in  water.  The  carbonates  of  the 
metal  have  either  a  blue  or  a  green  color;  these  salts  are  insoluble  in 
water,  but  readily  soluble  in  diluted  acids,  with  effervescence.  With 
chlorine  the  metal  unites  in  two  proportions,  forming  cuprous  chlo- 
ride (CugClg)  and  the  dichloride,  or  cupric  chloride  (CuClg) ;  the 
former  of  which  is  white  and  insoluble,  while  the  latter  has  a  green 
color  and  is  readily  soluble. 

The  property  of  forming  blue  and  green  compounds  is  somewhat 
peculiar  to  copper ;  yet  some  of  the  preparations  of  a  few  other 
metals  have  one  or  the  other  of  these  colors.  Thus,  some  of  the 
compounds  of  nickel,  sesquioxide  of  chromium,  and  uranium  oxide 
are  green,  while  some  of  the  salts  of  cobalt  are  blue.  Copper,  how- 
ever, is  the  only  one  of  these  metals  likely  to  be  met  with  in  medico- 
legal investigations,  and  is  readily  distinguished  from  the  others  in 
that  when  its  salts  are  moistened  with  a  diluted  acid  and  placed  in 
contact  with  a  piece  of  bright  iron  or  steel,  they  impart  to  the  iron 
a  coating  of  metallic  copper,  readily  recognized  by  its  peculiar  red 
color. 

Salts  of  copper,  when  heated  in  the  inner  blow-pipe  flame,  impart 
a  beautiful  green  coloration  to  the  outer  flame.  When  mixed  with 
dry  sodium  carbonate  or  potassium  cyanide  and  heated  on  a  charcoal 
support,  in  the  reducing  blow-pipe  flame,  they  yield  red  particles  of 
metallic  copper. 

Of  Solutions  of  Copper. — The  soluble  salts  of  copper  com- 


388  COPPER. 

municate  their  color  to  solutions,  even  when  highly  diluted.  In  the 
case  of  the  sulphate,  the  blue  color  is  quite  perceptible  in  fifty  grains 
of  a  solution  containing  only  1-lOOOth  of  its  weight  of  oxide  of 
copper ;  the  same  quantity  of  a  l-5000th  solution  exhibits  a  slight 
bluish  tint.  In  larger  quantities  of  the  liquid,  the  color  of  this 
salt  is  quite  perceptible  in  solutions  much  more  dilute  than  those 
just  mentioned.  Solutions  of  salts  of  copper,  when  not  too  dilute, 
slightly  redden  blue  litmus-paper;  they  have  an  astringent,  metallic 
taste,  and,  when  evaporated  spontaneously,  leave  the  salt  in  its  crys- 
talline state. 

In  the  following  investigations  of  the  different  tests  for  copper 
when  in  solution,  pure  aqueous  solutions  of  the  sulphate  were  em- 
ployed. The  fractions  indicate  the  quantity  of  monoxide  of  copper, 
CuO,  or  its  equivalent,  present  in  one  grain  of  the  solution.  One 
part  of  the  oxide  corresponds  to  3.141  parts  of  pure  crystallized 
sulphate  of  copper. 

1.  Sulphuretted  Hydrogen. 

Sulphuretted  hydrogen  gas  and  the  alkaline  sulphides  throw 
down  from  solutions  of  salts  of  copper,  even  in  the  presence  of  a 
free  acid,  a  precipitate  of  copper  sulphide,  CuS,  which  as  first  pro- 
duced has  a  brown  color,  but  sooner  or  later  becomes  brownish  or 
greenish-black.  The  precipitate  is  slightly  soluble  in  large  excess  of 
ammonium  sulphide,  but  insoluble  in  the  fixed  alkaline  sulphides, 
and  in  the  caustic  alkalies.  It  is  only  sparingly  soluble  in  cold  con- 
centrated nitric  acid ;  but  upon  the  application  of  heat,  even  when 
the  acid  is  somewhat  dilute,  it  readily  dissolves,  forming  a  blue  solu- 
tion of  the  nitrate,  with  more  or  less  copper  sulphate.  It  is  slowly 
dissolved  by  hot  concentrated  hydrochloric  acid,  with  the  formation 
of  the  monochloride  of  copper ;  concentrated  sulphuric  acid  has  but 
little  action  upon  it  in  the  cold,  but  it  is  decomposed  by  the  hot  acid. 
In  its  dry  state,  sulphide  of  copper  has  a  greenish-black  color;  when 
exposed  to  moist  air,  it  slowly  absorbs  oxygen,  and  becomes  converted 
into  copper  sulphate. 

In  examining  the  limit  of  this  test,  ten  grains  of  the  copper 
solution  were  submitted  to  a  slow  stream  of  the  washed  sulphu- 
retted gas. 

1,   1-lOOth  solution  of  copper  oxide  (=yV  gi'ain  CuO)  yields  an 
immediate  deep  brown  precipitate,  which  soon  becomes  brown- 


SULPHURETTED    HYDROGEN    TEST.  .'.81) 

• 

isli-l)l:i(k.  After  standing  sonu!  time,  tlie  precipitate  entirely 
separates  as  a  copious,  black  deposit,  leaving  the  solution  per- 
fei'tly  colorless. 

2.  1-lOOOth  solution  yields  at  iirst  a  brown   mixture,  from  which, 

after  a  time,  a  brownish-black  deposit  separates,  leaving  the 
liquid  of  a  brownish  color.  After  standing  some  hours,  the 
liquid  becomes  colorless,  and  the  deposit  acquires  a  greenish- 
black  color. 

3.  l-5000th  solution:   the  solution   immediately  assumes  a  browu 

color,  and  soon  becomes  turbid  ;  after  several  hours  a  quite  fair 
greenish-black  deposit  separates. 

4.  1-1 0,000th  solution  :  the  liquid  immediately  acquires  a  brownish 

color,  which  soon  deepens ;  after  the  mixture  has  stood  about 
twenty-four  hours,  it  yields  a  greenish-brown  deposit.    '' 

5.  l-25,000th  solution  :   the  liquid  immediately  assumes  a  yellow 

brown  color,  which  soon  changes  to  brown;  in  twenty-four 
hours  a  satisfactory  light  brown  deposit  has  formed. 

6.  l-50,000th  solution:  almost  immediately  the  liquid   assumes  a 

yellowish  color,  and  soon  becomes  brownish-yellow;  in  twenty- 
four  hours  quite  perceptible  brownish  flakes  have  separated,  and 
the  liquid  has  a  brownish  color. 

7.  l-100,000th  solution:  after  several  minutes  the  liquid  acquires 

a  faint  yellowash  color,  which  soon  becomes  quite  distinct;  in 
twenty-four  hours  it  has  a  faint  brownish  hue,  but  there  is  no 
precipitate. 
This  reagent  also  produces  brownish  precipitates  with  several 
other  metals,  but  most  of  these  are  extremely  rare  and  not  likely  to 
be  met  with  in  medico-legal  investigations.  The  transition  of  color 
observed  in  the  sulphide  of  copper  is  somewhat  peculiar  to  this  sub- 
stance, especially  when  the  metal  is  present  in  quite  notable  quantity. 
When  the  sulphide  is  moistened  with  hydrochloric  acid  and  touched 
for  a  little  time  with  a  bright  sewing-needle,  the  latter  becomes 
coated  with  metallic  copper  of  its  peculiar  color.  The  true  nature 
of  the  precipitate  may  also  be  established  by  dissolving  it,  by  the 
aid  of  heat,  in  a  little  nitric  acid,  evaporating  the  solution  to  dry- 
ness, dissolving  the  residue  in  a  little  water,  and  testing  the  solution 
with  ammonia  or  potassium  ferrocyanide,  in  the  manner  described 
hereafter. 

Neither  nickel,  chromium,  uranium,  nor  cobalt — metals  which, 


390  COPPER, 

like  copper,  have  the  property  of  forming  green  or  blue  salts — will 
yield  a  precipitate  from  acid  or  neutral  solutions  when  treated  with 
sulphuretted  hydrogen  gas. 

2.  Ammonia. 

This  reagent  produces  in  solutions  of  salts  of  copper  a  blue  or 
greenish -blue,  amorphous  precipitate,  which  is  readily  soluble,  to  a 
deep  blue  solution,  in  excess  of  the  precipitant.  With  very  dilute 
cupreous  solutions  the  reagent  may  fail  to  produce  a  precipitate,  but 
the  liquid  immediately  assumes  a  blue  color,  which  is  readily  destroyed 
upon  the  addition  of  a  free  acid. 

1.  Ywo  g'^ai'^  of  copper  oxide,  in  one  grain  of  fluid,  yields  a  copious 

precipitate,  which  with  excess  of  the  reagent  dissolves  to  an 
in^nsely  blue  solution. 

2.  Yoo~o  gi'aii^  yields  a  blue,  flocculent  deposit,  which  readily  dis- 

solves in  excess  of  the  precipitant,  forming  a  distinctly  blue 
liquid. 

3.  gQ^QQ  grain,  with  a  very  minute  quantity  of  the  reagent,  yields 

a  very  distinct  precipitate :  this  precipitate  is  best  obtained  by 
exposing  the  copper  solution  to  the  vapor  of  ammonia ;  when 
the  precipitate  is  dissolved  in  excess  of  the  reagent,  the  mixture 
has  a  just  perceptible  blue  tint. 

4.  Yo.VoT  g^'^io,  when  exposed  to  the  vapor  of  ammonia,  yields  a 

distinct  precipitate,   which,    when  dissolved  in  excess  of   the 
precipitant,  forms  an  apparently  colorless  liquid.     Ten  grains 
of  the  solution  have  a  quite  distinct  blue  color.      This  blue 
color  is  quite   obvious  in   much   more  dilute  solutions,   when 
larger  quantities  of  the  liquid  are  examined. 
Normal  solutions  of  salts  of  nickel  yield  with  ammonia  a  par- 
tial precipitate  of  green,  hydrated  oxide  of  nickel,  which,  like  the 
copper  precipitate,  is  readily  soluble  in  excess  of  the  reagent,  forming 
a  deep  blue  solution.     Solutions  of  salts  of  cobalt  yield  with  the 
reagent  a  blue  precipitate,  which  dissolves  in  excess  of  the  precip- 
itant, forming  a  reddish-brown  liquid.     From  solutions  of  the  salts 
of  sesquioxide  of  chromium,  ammonia  throws  down  a  bluish-green 
precipitate,  which  is  slightly  soluble  in  excess  of  the  reagent,  with 
the  formation  of  a  pink  solution.     Salts  of  uranium  yield  with  the 
reagent  a  yellow  precipitate,  which  is  insoluble  in  excess  of  the 
precipitant. 


REACTION    WITH    TIIH    TIXKl)    ALKALIEH.  391 

3.    rotfusninm  and  Sod  in  in  IlydrateH. 

Tlie  fixt'd  caustic  alkalies  throw  down  (Vorn  solutions  of  salts  of 
copper  a  blue  amorphous  j)rccipitate  of"  cupric  hydrate,  or  hydrated 
oxide  of  copper,  CuOjIIjO,  which  is  insoluble  in  excess  of  the  pre- 
cipitant, but  readily  soluble  in  acids,  even  acetic  acid.  On  boiling 
the  mixture  containing  an  excess  of  the  reagent,  the  precipitate 
speedily  becomes  anhydrous  and  of  a  black  color:  this  change  is 
slowly  ettected  even  at  ordinary  temperatures. 

The  reaction  of  these  reagents  is  much  modified  by  the  presence 
of  certain  organic  substances.  Thus,  in  a  solution  of  the  sulphate 
of  copper  containing  grape-sugar,  the  precipitate  is  readily  soluble  in 
excess  of  the  precipitant,  forming  a  deep  blue  solution,  from  which 
the  whole  of  the  copper  is  thrown  down  by  boiling,  in  the  form  of 
a  yellow  or  red  powder  of  cuprous  oxide,  or  suboxide  of  copper, 
CujO.  In  the  presence  of  tartaric  acid  the  reagent  may  fail  to 
produce  a  precipitate,  even  upon  boiling  the  mixture. 

1.  Yuu  gi'ain    of   copper   oxide,   in  one  grain    of    water,  yields   a 

copious,  blue,  gelatinous  deposit. 

2.  xFo¥  gi'ain  :  a  very  good,  flocculent  precipitate. 

3.  g-gVu"  gi'ain  yields  in  a  very  little  time  a  slight;  flocculent  pre- 

cipitate, which  soon  becomes  a  quite  fair  deposit. 

4.  xu.VoT  grain  :  after  a  little  time  a  just  perceptible  cloudiness, 

and  soon  a  quite  distinct,  flaky  deposit. 

These  reagents  also  produce  a  blue  precipitate  in  solutions  of 
salts  of  cobalt,  which  is  insoluble  in  excess  of  the  reagent ;  but 
when  this  mixture  is  boiled,  the  precipitate  is  changed  into  a  brown- 
ish or  reddish  deposit.  Solutions  of  the  sesquioxide  of  chromium 
yield  with  the  reagent  a  bluish-green  precipitate,  readily  soluble  in 
excess  of  the  preci}>itant,  forming  a  greenish  liquid,  from  which,  by 
continued  boiling,  the  whole  of  the  chromium  is  reprecipitated  as 
green,  hydrated  sesquioxide  of  the  metal.  These  are  the  only  two 
metals  which  yield  with  these  reagents  precipitates  the  color  of 
which  might  be  confounded  with  that  of  the  copper  precipitate. 

Potassium  and  sodium  carbonate  occasion  in  aqueous  solutions  of 
cupreous  salts  a  greenish-blue,  amorphous  precipitate  of  hydrated 
oxycarbouate  of  copper,  CuO,CuC03,H20,  which  is  sparingly  solu- 
ble, to  a  bluish  liquid,  in  excess  of  the  precipitant.  If  an  excess 
of   the  reagent  be  added  and  the  mixture  boiled,  the  precipitate 


392  COPPER. 

becomes  converted  into  black  anhydrous  cupric  oxide.  The  b'mit 
of  the  reaction  of  these  reagents  is  the  same  as  that  of  the  fixed; 
caustic  alkalies. 

4.  Potassium  Feri^ocyanide. 

This  reagent  throws  down  from  somewhat  strong  solutions  of 
salts  of  copper  a  reddish-brown,  amorphous  precipitate  of  ferro- 
cyanide  of  copper^  CugFeCyg,  which  is  insoluble  in  excess  of  the 
precipitant,  and  in  acetic  and  hydrochloric  acids,  but  sparingly 
soluble  in  ammonia  to  a  bluish-green  liquid,  from  which  it  is  re- 
precipitated  by  excess  of  acetic  acid.  From  more  dilute  solutions 
the  reagent  produces  a  purple  precipitate;  while  from  still  more 
dilute  solutions  it  fails  to  produce  a  precipitate,  but  the  mixture 
assumes  a  reddish  color. 

1.  Y^  grain  of  copper  oxide  yields  a  copious,  reddish-brown,  gelat- 

inous precipitate. 

2.  xoVq-  grain  :  an  immediate  purple  precipitate,  which  soon  becomes 

a  quite  good,  reddish-brown  deposit. 

3.  x¥,'on'  grain  :  a  reddish,  flocciilent  turbidity. 

4.  -js-.TDT  grain  yields  a  slight  cloudiness;  when  viewed  over  white 

paper,  the  mixture  exhibits  a  distinct  reddish  color. 

When  jive  grains  of  a  1-1 00,000th  solution  are  treated  with  a 
small  quantity  of  the  reagent,  the  mixture  presents  a  quite  distinct 
reddish  color.  This  color  is  readily  observed  even  in  more  dilute 
solutions,  when  larger  quantities  are  examined. 

Potassium  ferrocyanide  also  produces  in  solutions  of  uranic  salts 
a  precipitate  very  similar  in  color  to  that  of  the  ferrocyanide  of 
copper.  But  the  uranium  precipitate  is  changed  to  a  yellow  com- 
pound upon  the  addition  of  excess  of  ammonia ;  whereas,  as  before 
stated,  the  copper  ferrocyanide  is  soluble  to  a  limited  extent  in  ex- 
cess of  this  alkali,  yielding  a  bluish-green  liquid.  Moreover,  solu- 
tions of  copper  are  readily  distinguished  from  those  of  uranium  by 
their  behavior  with  sulphuretted  hydrogen  and  ammonia,  as  already 
pointed  out.  Copper  and  uranium  are  the  only  metals  that  yield 
reddish-brown  precipitates  with  potassium  ferrocyanide. 

The  reaction  of  this  reagent  with  solutions  of  salts  of  copper  is 
much  modified  by  the  presence  of  even  minute  quantities  of  iron, 
with  which  it  produces  a  blue  precipitate. 


IRON  TEST.  ;i93 


6.  Iron  Test. 


When  a  piece  of  bright  iron  or  steel  is  immersed  in  a  solution  of 
a  salt  of  copper,  it  sooner  or  later  decomposes  the  salt  and  receives  a 
conting  of  metallic  copper,  having  tlu?  characteristic  color  of  the 
metal ;  at  the  same  time,  a  salt  of  iron,  containing  the  acid  previously 
combined  with  the  copper,  is  formed.  This  reaction,  especially  from 
dilute  solutions,  is  mucli  facilitatcil  by  the  presence  of  a  little  free 
sul])huric  or  hydrochloric  acid. 

In  examining  the  limit  of  this  test,  a  single  grain  of  the  copper 
solution,  placed  in  a  watch-glass,  was  acidulated  with  sulphuric  acid, 
and  a  small  portion  of  a  bright  sewing-needle  introduced  into  the 
mixture;  in  the  very  dilute  solutions  the  length  of  the  needle  did 
not  exceed  -^  of  an  inch.  It  is  obvious  that  the  thickness  of  the 
deposit  from  a  given  quantity  of  copper,  and  consequently  the  deli- 
cacy of  the  test,  will  depend  very  much  upon  the  extent  of  surface 
over  which  the  metal  is  distributed. 

1.  Yuir  grain  of  copper  oxide  yields  a  very  fine  coating. 

2.  YUou  grain  :  in  a  little  time  the  needle  acquires  a  very  satisfactory 

deposit. 

3.  xTj.-l-oiT  grain  :  in  a  few  minutes  the  needle  presents  a  reddish  tint, 

and  in  fifteen  minutes  receives  a  satisfactory  coating. 

4.  ^ovoiTd  grain  :  after  several  minutes  the  neeille  exhibits  a  just  j)er- 

ceptible  reddish  hue,  which  improves,  and  after  an  hour  becomes 
perfectly  satisfactory. 

By  allowing  the  needle  to  remain  in  the  acidulated  liquid  for 
several  hours,  satisfactory  deposits  may  be  obtained  from  solutions 
much  more  dilute  than  the  last-mentioned.  The  true  color  of  very 
thin  deposits  is  best  determined  by  the  aid  of  a  hand-lens. 

It  need  hardly  be  remarked  that  this  reaction  is  peculiar  to 
copper.  The  cupreous  nature  of  the  deposit  may  be  shown  by  dis- 
solving out  the  iron  from  the  coated  needle  with  diluted  sulphuric 
acid,  and  then  dissolving  the  washed  coating  in  a  little  nitric  acid, 
evaporating  the  solution  to  dryness,  redissolving  the  residue  in  a  few 
drops  of  water,  and  testing  the  liquid  with  potassium  ferrocyanide. 

6.  Platinum  arid  Zinc  Test. 

When  a  solution  of  a  salt  of  copper  is  acidulated  with  hydro- 
chloric or  sulphuric  acid,  and  placed  in  a  platinum  dish,  and  then  a 


394  COPPER. 

fragment  of  bright  zinc  placed  in  the  liquid,  the  cupreous  compound 
quickly  undergoes  decomposition,  with  the  deposition  of  a  coating  of 
metallic  copper,  of  its  peculiar  color,  upon  the  platinum  covered  by 
the  liquid. 

1.  YF¥  grain  of  copper  oxide  in  one  grain  of  fluid,  when  treated 

after  this  method,  yields  a  very  fine  deposit. 

2.  YoVo"  E^^^^  •  after  a  few  minutes  the  platinum  exhibits  a  very 

satisfactory  coating. 

3.  gQ^QQ  grain  :  after  several  minutes  there  is  a  quite  distinct  deposit. 
This  method  will  not  serve  for  the  detection  of  as  minute  quan- 
tities of  copper  as  the  iron  test,  since  in  its  application  the  metal  is 
distributed  over  a  larger  surface  than  when  the  iron-method  is  em- 
ployed. If  the  washed  deposit  be  moistened  with  a  few  drops  of 
caustic  ammonia,  the  liquid  slowly  acquires  a  blue  color,  due  to  the 
formation  of  a  soluble  compound  of  the  metal. 

7.  Potassium  Ar senile. 

This  reagent  throws  down  from  neutral  solutions  of  salts  of 
copper,  when  not  too  dilute,  a  bright  green  precipitate  of  cupric 
arsenite,  CuHAsOg,  known  also  as  Scheele's  green.  This  precipitate 
is  readily  soluble  in  ammonia  and  in  free  acids. 

1.  Yw  gi^ain  of  copper  oxide,  in  one  grain  of  water,  yields  a  copious 

precipitate. 

2.  YcToo"  grain  :  a  quite  good, yellowish-green  deposit. 

3.  YF.Wo  gi'a-hi :  after  a  little  time  the  mixture  becomes  decidedly 

turbid ;  but  the  green  color  is  not  perceptible.     With  larger 

quantities    of   the   solution    the   reagent   produces   satisfactory 

results,  even  in  much  more  dilute  solutions. 

The  production  of  a  bright  green  precipitate  by  this  reagent  is 

quite  characteristic  of  copper.     However,  solutions  of  salts  of  nickel 

yield  with  the  reagent  a  pale  green  deposit,  which,  like  the  copper 

precipitate,  is  readily  soluble  in  ammonia  and  in  acetic  acid. 

8.  Potassium  Chr ornate. 

Monochromate  of  potassium,  when  added  in  excess  to  somewhat 
strong  solutions  of  salts  of  copper,  produces  a  reddish-brown  pre- 
cipitate of  cupric  chromate,  which  is  readily  soluble  in  ammonia, 
forming  a  beautiful  green  liquid ;  the  precipitate  is  also  soluble  in 
acetic  acid,  and  in  excess  of  the  copper  solution.     From  more  dilute 


POTASSIUM    lODIDK   TEST. 


396 


solutions    the    roagciit    throws   down    a   yoUow  or   greenish-yellow 
<leposit. 

1-    k'mV  J^'"^'"  ^^  copper  oxide,  in  one  grain  of  water,  yields  a  v(.'ry 
copious,  reddish-brown,  ainorjjhous  precii)itate. 

2.  ^JL^ii    ij;rain :    a  copious,  yellow  deposit,   which   soon   assdiiies  a 
greenish-yellow  color. 

3.  -^Y^-^  grain  yields  an   immediate  bluish-yellow  turbidity,  and 

soon  a  quite  satisfactory  greenish-yellow  precipitate. 

4.  -^i^^  grain  :  after  several  minutes  a  quite  perceptible  turbidity. 

Potassium  dichromate  fails  to  produce  a  precipitate,  even  in  con- 
centrated solutions  of  salts  of  copper. 

9.  Potassium  Ferricyanide. 

Normal  solutions  of  salts  of  copper  yield  w^ith  this  reagent  a 
brownish-yellow  or  greenish-yellow  amorphous  precipitate  of  cu]3ric 
ferricyanide,  which  is  insoluble  in  acetic  acid,  but  is  readily  soluble 
in  ammonia,  forming  a  beautiful  green  fluid. 

1.  ^  grain  of  copper   oxide   yields   a  copious,  brownish-yellow 

precipitate. 

2.  Yimr  g^'^^"  '•  '•■'^  ^^^T  S^od  deposit. 

3.  ^i-j_  grain  :  a  rather  good,  greenish-yellow  precipitate. 

4.  Yij-lj-j^  grain  yields  a  greenish  turbidity. 

The  production  of  a  brownish  or  greenish-yellow  precipitate  by 
this  reagent  is  common  to  solutions  of  several  other  metals  besides 

copper. 

10.  Potassium  Iodide. 

This  reagent  produces  in  solutions  of  salts  of  copper  a  yellow^  or 
brownish-yellow  precipitate,  which  soon  changes  to  a  brownish  or 
yellowish-whitedeposit  of  cuprous  iodide,  Cuglj;  at  the  same  time 
iodine  is  set  free,  and  dissolves  in  any  excess  of  the  reagent  present: 
2CuSO,  -f  4KI  =  2K2SO,  +  Cu J2  +  I2.  The  precipitate  is  insolu- 
ble in  acetic  acid,  but  is  readily  soluble  to  a  deep  blue  solution  in 

ammonia. 

1.  _J__  grain   of  copper  oxide   yields   a   copious,    brownish-yellow 

precipitate,  which  soon  acquires  a  yellowish-white  color. 

2.  ^-jig-g-  grain  :  a  quite  good  deposit. 

3.  ^__  grain  :    the  liquid   assumes  a  yellow  color,  then   becomes 

turbid,  and  after  a  short  time  throws  down  small  granules. 


396  COPPER. 

4,  Y^.VoT  grain  :  after  a  little  time  the  mixture  acquires  a  yellow 
color,  then  becomes  turbid. 
The  production  bv  this  reagent  of  a  brownish  or  yellowish  pre- 
cipitate, which  is  readily  soluble  in  ammonia  to  a  deep  blue  solution, 
is  quite  peculiar  to  solutions  of  copper. 

Guaiacum  Test. — If  a  solution  of  a  salt  of  copper  to  which  a 
little  common  salt  has  been  added  be  poured  gently  down  the  side 
of  a  test-tube  containing  an  alcoholic  solution  of  guaiacum,  a  blue 
color  is  produced  at  the  junction  of  the  two  liquids,  even  when  onlv 
a  minute  trace  of  copper  is  present ;  and  if  in  larger  quantity,  the 
whole  liquid  becomes  blue  on  agitation.  In  this  manner,  according 
to  E.  Purgottij  who  first  observed  the  reaction  (1878),  0.001  milli- 
gramme of  copper  sulphate  will  yield  a  blue  coloration. 

In  applying  this  test  it  must  be  borne  in  mind  that  ferric  com- 
pounds and  certain  other  substances  have  also  the  property  of  bluing 
a  like  solution  of  guaiacum.  These  objections  may,  for  the  most 
part  at  least,  be  answered  by  first  adding  the  copper  solution  to  the 
guaiacum  tincture,  and  then,  if  no  color  is  developed,  adding  to  the 
mixture  a  minute  crystal  of  sodium  chloride,  when  the  crystal  will 
become  surrounded  with  a  deep  blue  coloration,  even  if  only  a  very 
minute  quantity  of  the  metal  is  present. 

Detection  of  the  Acid. — The  tests  now  considered  would, 
of  course,  serve  only  for  the  detection  of  the  metal  of  the  copper 
compound,  and  would  not  indicate  the  acid  with  which  it  was  com- 
bined. The  presence  of  sulphuric,  hydrochloric,  or  nitric  acid,  when 
combined  with  the  metal,  could  be  shown  in  the  manner  already 
described  under  the  special  consideration  of  these  acids. 

The  presence  of  acetic  acid,  as  in  the  case  of  verdigris,  could  be 
shown  by  boiling  the  cupreous  salt  with  a  small  quantity  of  a  mix- 
ture of  about  equal  volumes  of  strong  sulphuric  acid  and  alcohol, 
when  acetic  ether  of  its  characteristic  odor  would  be  evolved. 

Sepaeatiox  from  OEaAJjTEc  Mixtures. 

Suspected  Solutions. — The  soluble  salts  of  copper  are  more  or 
less  decomposed,  with  the  precipitation  of  oxide  of  the  metal  in 
combination  with  organic  matter,  by  various  animal  and  vegetable 
principles.     A   portion   of  the  clear   liquid,   after   concentration,   if 


SEPARATION   FROM   ORGANIC   MIXTURES.  397 

deemed  best,  may  be  slightly  acidulated  with  Kulplmric  acid,  and 
a  portion  of  a  bright-sc\vin<i;  needle  placed  in  the  mixture,  the 
immersion  being  contimicd  I'or  several  hours  if  necessary.  Any 
metallic  deposit  thus  obtained  may  be  washed  and  confirmed  by 
dissolving  the  needle  in  diluted  sulphuric  acid,  and  afterward  the 
washed  coating  in  nitric  acid,  in  the  manner  already  described  when 
considering  the  iron  test. 

In  the  application  of  this  test,  it  should  be  borne  in  mind  that 
the  needle  \m\y  after  a  time,  even  in  the  absence  of  copper,  present  a 
reddish  appearance,  due  to  the  formation  of  a  coating  of  iron  oxide. 
A  deposit  of  this  kind,  however,  may  be  readily  distinguished  from 
that  produced  by  copper,  even  in  most  instances  by  examining  it 
with  a  hand-lens.  Should  the  iron  test  reveal  the  presence  of  cop- 
per, other  portions  of  the  liquid  may  be  examined  by  some  of  the 
other  tests  for  the  metal.  Most  of  these  tests,  however,  have  their 
action  readily  interfered  with  by  the  presence  of  organic  matter. 

Should  the  liquid  presented  for  examination  be  mixed  with  much 
solid  organic  matter,  the  mixture,  after  the  addition  of  water  if 
necessary,  may  be  gently  heated  for  some  time,  and  a  portion  of 
the  filtered  liquid  then  examined  in  the  manner  before  described. 
Should  there  be  a  failure  thus  to  detect  the  poison,  there  would  be 
little  doubt  of  its  entire  absence.  Yet,  the  solids  separated  from 
the  liquid  by  filtration  may  be  boiled  for  about  fifteen  minutes  with 
water  containing  a  little  hydrochloric  acid,  and  the  solution  thus 
obtained  be  examined  either  by  the  iron  test  or  by  sulphuretted 
hydrogen  gas. 

Contents  of  the  Stomach.— These  are  carefully  transferred  to  a 
clean  porcelain  dish,  and  the  inside  of  the  stomach  well  scraped, 
the  scrapings  being  added  to  the  matters  in  the  dish.  The  contents 
of  the  dish,  after  the  addition  of  water  if  necessary,  are  strongly 
acidulated  with  hydrochloric  acid,  and  gently  boiled  until  the  organic 
solids  are  well  broken  up.  The  cooled  liquid  is  then  filtered,  the 
filtrate  somewhat  concentrated,  again  filtered,  and  then  exposed  to  a 
slow  stream  of  sulphuretted  hydrogen  gas,  as  long  as  a  precipitate  is 
produced,  by  which  any  copper  present  will  be  thrown  down  as  sul- 
phide of  the  metal.  When  the  precipitate  has  completely  subsided, 
it  is  collected  on  a  filter,  washed,  and  then  dissolved,  by  the  aid  of 
heat,  in  a  small  quantity  of  diluted  nitric  acid.  On  now  treating 
the  solution  with  a  drop  or  two  of  sulphuric  acid  and  cautiously 


398  COPPER. 

evaporating  it  to  dryness,  the  metal,  if  present,  will  be  left  as  blue 
copper  sulphate.  The  residue  thus  obtained  is  dissolved  in  a  small 
quantity  of  warm  water,  and  the  filtered  solution  examined  for 
copper  by  the  ordinary  reagents,  especially  by  the  iron  and  ammonia 
tests. 

Should  the  precipitate  produced  by  sulphuretted  hydrogen  be 
small  in  quantity  and  apparently  contain  much  organic  matter,  the 
residue  obtained  after  solution  in  nitric  acid  and  evaporation  is 
moistened  with  concentrated  nitric  acid  and  heated  until  the  organic 
matter  is  entirely  destroyed.  The  dry  mass  is  then  treated  with  a 
little  diluted  nitric  acid,  the  liquid  expelled  by  a  moderate  heat,  the 
residue  dissolved  in  a  little  pure  water,  and  the  solution  tested. 

From  the  Tissues. — For  the  purpose  of  examining  any  of  the 
soft  tissues  of  the  body  for  absorbed  copper,  the  organ,  as  a  portion 
of  the  liver  cut  into  small  pieces,  is  made  into  a  paste  with  pure 
nitric  acid  diluted  with  three  or  four  volumes  of  water,  and  the  mix- 
ture gently  boiled,  with  the  occasional  addition  of  small  quantities 
of  powdered  potassium  chlorate,  until  the  whole  becomes  perfectly 
homogeneous.  It  is  then  diluted  with  w^ater,  allowed  to  cool,  and 
the  filtered  liquid  evaporated  to  dryness.  The  residue  thus  obtained, 
placed  in  a  thin  porcelain  capsule,  is  covered  with  concentrated  nitric 
acid,  a  little  potassium  chlorate  added,  and  the  liquid  evaporated  by 
a  moderate  heat ;  the  heat  is  then  increased  and  continued  until  the 
organic  matter  is  entirely  destroyed,  when  the  mass  will  assume  a 
nearly  white  color.  On  boiling  this  residue  in  nitric  acid  containing 
a  little  water,  any  copper  present,  together  with  the  small  quantity 
of  iron  which  is  usually  present  in  the  tissues,  will  be  taken  up  in 
a  soluble  form.  This  solution  is  carefully  evaporated  to  dryness,  to 
expel  the  excess  of  nitric  acid,  the  residue  dissolved  in  a  little  warm 
water,  and  tested  in  the  usual  manner.  Should  the  solution  contain 
iron,  any  copper  present  may  be  separated  from  that  metal  by  acid- 
ulating the  liquid  with  hydrochloric  acid  and  treating  it  with  sul- 
phuretted hydrogen,  when  the  copper  will  be  thrown  down  as  sul- 
phide of  the  metal,  while  the  iron  will  remain  in  a  soluble  form ; 
the  precipitated  copper  sulphide  is  then  collected  on  a  filter,  washed, 
dissolved  in  a  little  nitric  acid,  and  the  solution  examined  in  the 
manner  already  indicated. 

Another  method   for  the  separation  of  iron,  when  present  in  a 
liquid  with  copper,  is  to  treat  the  solution  with  excess  of  ammonia. 


SKPARATION    FROM    TIIK    URINE.  399 

when  tlio  foritier  metal  will  be  precipitated  as  liydrated  scsqiiioxide 
of  iron,  while  the  copper  will  remain  in  i^olntion,  fbrminfj  a  deep 
hlne  liqnid.  After  removing  the  iron  precipitate  by  a  filter,  a  j)or- 
tion  of  the  filtrate  may  be  slightly  acidnlated  with  acetic  acid,  and 
tested  with  a  solution  of  potassium  ferrocyanide. 

In  a  Ciise  of  poisoning  by  copper  sulphate,  M.  Malagutti 
readily  detected  the  metal  in  a  portion  of  the  liver  of  the  deceased; 
and  also  in  about  two  ounces  of  the  urine.  [Jour,  de  Chim.  Med., 
April,  1862,  209.) 

In  an  instance  in  which  two  women  had  suffered  vs^ith  symptoms 
resembling  those  produced  by  copper  compounds,  and  almost  inces- 
sant vomiting  for  two  or  three  weeks,  the  bodies  when  exhumed 
several  months  after  death  were  found  in  a  remarkable  state  of  pres- 
ervation, and  the  liver  in  each  case  contained  0.120  gramme  (1.85 
grains)  and  0.080  gramme  (1.23  grains)  respectively  of  copper. 
{Ibid.,  1874,  504.) 

In  experiments  on  animals,  in  regard  to  the  elimination  of  the 
salts  of  copper,  I.  L.  Orfila  administered  small  quantities  of  the 
sulphate,  mixed  with  food,  to  dogs  for  fifteen  days,  and  found  the 
metal  in  the  liver,  in  the  tissue  of  the  stomach,  and  in  the  lungs  sixty 
days  after  it  had  been  administered.  But  the  metal  was  found  in 
the  urine  for  only  a  few  days  after  it  had  ceased  to  be  taken ;  and 
even  in  some  instances  it  was  not  detected  after  the  lapse  of  twenty- 
four  hours.     ( Orfila' s  Toxicologie,  i.  791.) 

MM.  Bournville  and  Yvon  relate  the  ca.se  of  an  epileptic  patient 
who  was  given,  during  a  period  of  four  months,  forty-three  grammes 
(six  hundred  and  fifty  grains)  of  the  ammonio-sulphate  of  co})per. 
The  medicine  was  then  discontinued,  and  at  the  end  of  three  months 
the  patient  died  from  tuberculosis.  On  inspection,  the  stomach  and 
intestines  presented  no  appearance  which  could  be  attributed  to  the 
copper  compound,  but  the  liver  contained  0.295  gramme  (four  and 
one-half  grains)  of  metallic  copper,  corresponding  to  1.166  gramme 
of  crystallized  sulphate  of  the  metal.  {Jour,  de  Chim.  Med.,  May, 
1875,"  236.) 

Froin  the  Urine. — About  five  ounces  or  more  of  the  urine  are 
evaporated  to  dryness,  and  the  organic  matter  of  the  residue  destroyed 
by  means  of  concentrated  nitric  acid  and  potassium  chlorate,  and 
subsequent  incineration.  The  ash  thus  obtained,  which  will  gener- 
ally contain  a  small  trace  of  iron,  is  dissolved  in  hot  diluted  nitric 


400  ZINC. 

acid,  and  the  liquid  evaporated.  Any  nitrate  of  copper  present  in 
the  residue  is  then  dissolved  in  a  small  quantity  of  water,  and  the 
solution  examined  in  the  usual  manner. 

In  six  cases  of  non-fatal  poisoning  by  salts  of  copper,  collected 
by  M.  Kletzinsky,  the  metal  was  found  in  the  urine  as  long  as  the 
patients  experienced  any  active  symptoms.  When  these  ceased,  the 
metal  disappeared  from  the  urine ;  but  it  continued  to  be  discharged 
with  the  faeces.     (Thudichum,  Pathology  of  the  Urine,  409.) 

Quantitative  Analysis. — Copper  is  usually  estimated  as 
cupric  oxide,  or  monoxide  of  the  metal.  The  solution  is  heated 
to  about  the  boiling  temperature,  and  a  solution  of  potassium  or 
sodium  hydrate  added  as  long  as  a  precipitate  is  produced,  after 
which  the  heat  is  continued  for  some  minutes.  When  the  mixture 
has  cooled  and  the  supernatant  liquid  become  perfectly  clear,  the 
precipitate  is  collected  on  a  filter  of  known  ash,  washed  with  warm 
water,  and  dried.  It  is  then,  as  far  as  practicable,  separated  from 
the  filter,  strongly  ignited  in  an  equipoised  platinum  capsule,  and 
the  ash  of  the  filter,  which  has  been  burned  separately,  added  to  the 
ignited  mass ;  the  whole  is  then  allowed  to  cool,  and  quickly  weighed. 
When  the  quantity  of  precipitate  is  small,  it  may  be  ignited  along 
with  the  filter. 

Should  the  alkaline  liquid  separated  by  filtration  from  the  pre- 
cipitated oxide  of  copper  have  a  blue  color,  it  is  boiled  with  a  little 
grape-sugar,  when  any  copper  still  present  will  be  thrown  down  as 
suboxide  of  the  metal ;  this  is  collected,  washed,  moistened  with 
nitric  acid,  the  liquid  evaporated,  and  the  residue  ignited,  when  the 
copper  will  remain  as  cupric  oxide.  One  hundred  parts  by  weight 
of  anhydrous  monoxide  of  copper  correspond  to  314.21  parts  of 
pure  crystallized  sulphate  of  copper. 

Section  III. — Zinc. 

History  and  Chemical  Nature. — The  symbol  for  zinc  is  Zn,  its 
atomic  weight  65.2,  and  its  specific  gravity  about  7.  Zinc  is  found 
in  nature  under  several  forms  of  combination,  but  chiefly  as  car- 
bonate of  the  metal.  Zinc  is  a  bluish-white  metal  having  a  bright 
metallic  lustre,  very  brittle,  and,  when  fractured,  exhibits  a  crystal- 
line structure.     It  fuses,  according  to  Daniell,  at  412°  C.  (773°  F.), 


GENERAL  CHEMICAL  NATURE.  401 

and  at  a  red  heat  is  volatilized,  being  dissipated  in  the  form  of  a 
colorless  vapor,  which,  in  the  presence  of  air,  takes  fire  and  burns 
with  a  white  flame,  forming  oxide  of  zinc,  ZnO.  When  heated  on 
a  charcoal  support  before  the  reducing  blow-pipe  flame,  it  fuses, 
then  burns,  evolving  dense  white  fumes,  and  coating  the  charcoal 
with  a  yellow  incrustation,  which  on  cooling  becomes  white. 

Exposed  to  the  air,  at  ordinary  temperatures,  zinc  becomes  covered 
with  a  gray  coating  of  basic  carbonate  of  zinc.  The  metal  is  readily 
dissolved  by  nitric  acid,  with  the  formation  of  zinc  nitrate,  and  the 
evolution  of  either  suboxide  or  monoxide  of  nitrogen,  the  nature  of 
the  evolved  gas  depending  upon  the  strength  of  the  acid  employed. 
It  is  also  readily  soluble  in  diluted  sulphuric  and  hydrochloric  acids, 
with  the  formation  of  a  salt  of  zinc  and  the  evolution  of  hydrogen  gas. 
As  found  in  commerce,  metallic  zinc  is  liable  to  be  contaminated  with 
carbon,  arsenic,  sulphur,  antimony,  iron,  lead,  and  cadmium. 

Zinc  unites  with  oxygen  in  only  one  proportion,  forming  the 
monoxide.  This  forms  a  white,  amorphous  powder,  which  at  ele- 
vated temperatures  has  a  lemon-yellow  color.  The  salts  of  zinc, 
unless  they  contain  a  colored  acid,  are  colorless.  They  are  for  the 
most  part  readily  soluble  in  water,  and  their  normal  solutions  have  a 
slightly  acid  reaction.  When  intimately  mixed  with  sodium  carbon- 
ate, and  heated  before  the  blow-pipe  on  a  charcoal  support,  the  salts 
of  zinc  are  readily  decomposed,  with  the  formation  of  an  incrusta- 
tion, over  the  charcoal,  of  oxide  of  zinc. 

When  taken  into  the  stomach,  metallic  zinc  is  destitute  of 
poisonous  properties,  at  least  so  long  as  it  retains  its  metallic  state; 
but  all  the  preparations  of  this  metal  are  more  or  less  poisonous ; 
they  are,  however,  less  active  than  the  compounds  of  lead  and  copper. 
The  continued  inhalation  of  the  oxide  of  zinc  has,  in  several  in- 
stances, given  rise  to  serious  symptoms.  {Chem.  Gaz. ,  vin.  SQ2  ;  also 
Med.-Chir.  Rev.,  July,  1873,  254.)  MM.  Lechartier  and  Bellamy 
state  that  they  found  minute  traces  of  zinc  in  the  livers  of  various 
men  of  different  occupations  and  who  had  died  of  different  diseases; 
in  the  muscles  of  an  ox,  in  the  liver  of  a  calf,  and  in  the  eggs  of 
the  common  fowl ;  also  in  wheat,  maize,  barley,  and  beet-root.  ( Chem. 
News,  May,  1877,  182.) 

The  only  salts  of  zinc  requiring  notice  in  this  connection  are  the 
sulphate  and  chloride.  Poisoning  by  these  salts  has  been  of  rare 
occurrence,  and  has  been  chiefly  the  result  of  accident. 

26 


402  ZENC. 

Sulphate  of  zinc,  or  white  vitriol,  ZnSO^jHgOjGAq,  as  usually 
found  in  the  shops,  is  in  the  form  of  small,  colorless,  prismatic  crys- 
tals, which  have  a  strongly  astringent,  metallic  taste,  and  are  slightly 
efflorescent  in  dry  air.  At  100°  C.  (212°  F.)  the  crystallized  salt 
gives  up  six  molecules  of  water,  and  at  about  204°  C.  (400°  F.) 
becomes  anhydrous ;  at  a  bright  red  heat  it  is  entirely  decomposed, 
leaving  a  residue  of  zinc  oxide.  It  is  soluble  in  about  two  and  a 
half  times  its  weight  of  water  at  ordinary  temperatures ;  and  in 
less  than  its  own  weight  of  boiling  water.  It  is  insoluble  in  alcohol, 
ether,  and  chloroform. 

Chloride  of  zinc,  ZnClg,  is  readily  obtained  by  dissolving  zinc  in 
diluted  hydrochloric  acid,  and  evaporating  the  solution  to  dryness. 
In  its  anhydrous  state  it  forms  a  soft,  white,  very  deliquescent 
solid,  which  is  readily  fusible,  and  volatilizes  unchanged  at  a  strong 
red  heat,  condensing  sometimes  in  the  form  of  colorless,  crystalline 
needles.  It  is  soluble  in  water  in  all  proportions,  and  also  soluble 
in  alcohol  and  ether.  The  liquid  known  in  the  shops  under  the 
name  of  "  Sir  Wm.  Burnett's  disinfecting  fluid"  is  a  solution  of  this 
salt,  containing  about  two  hundred  grains  of  the  anhydrous  salt  in 
each  fluid-ounce.  Several  instances  of  poisoning  by  this  liquid  have 
been  reported. 

Symptoms. — Sulphate  of  zinc  has  frequently  been  administered 
in  doses  of  several  grains  daily  for  long  periods  without  producing 
any  ill  eflPects.  Dr.  Babington  even  gave,  in  one  instance,  thirty-six 
grains  of  the  salt,  three  times  a  day  for  three  weeks,  without  any 
noxious  symptom  having  appeared.  When,  however,  the  salt  is 
swallowed  in  doses  of  several  drachms  or  more,  it  may  produce  very 
speedy  and  violent  symptoms,  and  even  death.  The  usual  symptoms 
are  an  astringent  taste  in  the  mouth,  a  sense  of  constriction  and 
burning  in  the  throat  and  fauces,  nausea,  violent  vomiting,  intense 
pain  in  the  stomach  and  bowels,  frequent  purging,  small  and  fre- 
quent pulse,  great  anxiety,  and  coldness  of  the  extremities.  The 
intellect  usually  remains  clear. 

A  robust  woman,  aged  twenty-five  years,  swallowed,  by  mistake 
for  Epsom  salt,  a  solution  containing  an  ounce  and  a  half  of  zinc 
sulphate.  She  instantly  vomited,  and  then  became  affected  with 
almost  incessant  retching  and  purging  for  half  an  hour,  which  con- 
tinued afterward,  at  short  intervals,  for  three  hours.  There  was  also 
a  small  and  frequent  pulse,  extreme  prostration,  great  anxiety,  cold- 


PHYSIOLOGICAL.    EFFECTS.  403 

ness  of  the  body,  violent  pain  in  \\\v,  abdomen  and  limbs,  with  a  sense 
of  burning  in  the  throat  and  stomach,  and  (U'ath  ensued  in  thirteen 
hours  and  a  half  after  the  poison  had  been  taken.  A  sister  of  this 
woman,  aged  thirty-five  years,  took  at  the  same  time  a  similar  dose 
of  the  poison,  but  after  several  days  of  severe  illness  she  finally  re- 
covered. In  this  instance  the  vomiting  was  delayed  for  fifteen  min- 
utes, and  there  was  no  purging  for  ten  hours;  the  other  symptoms 
much  resembled  those  of  her  sister,  except  the  burning  sensation  in 
the  throat,  which  was  absent.  {Amer.  Jour.  Med.  Sci,  July,  1849, 
279;  from  Brit,  and  For.  Med.-Chir.  Rev.,  April,  1849.) 

A  case  of  slow  poisoning  by  the  sulphates  of  zinc  and  iron  has 
been  reported  by  Dr.  Wm.  Hcrapath.  {Chem.  News,  June,  1865,  288.) 
The  symptoms  were  a  sense  of  burning  heat  in  the  stomach,  fauces, 
and  gullet,  coppery  taste  in  the  mouth,  great  thirst  and  nausea  after 
eating  and  drinking,  followed  by  vomiting  after  from  half  an  hour 
to  an  hour.  After  death,  the  stomach  was  found  considerably  in- 
flamed in  the  cardiac  portion,  and  its  inner  surface  was  in  a  blistered 
state;  the  intestines  were  but  slightly  inflamed.  Traces  of  zinc  and 
iron  sulphates  were  found  in  the  vomited  matters,  and  also  in  the 
contents  of  the  lower  intestines ;  but  in  the  contents  of  the  stomach 
and  duodenum  only  sulphate  of  iron  was  found. 

.The  following  case  of  recovery  is  reported  by  Dr.  J.  W.  Ramsey. 
{3Ied.  and  Surg.  Rep.,  Feb.  1869,  178.)  A  woman  in  ordinary 
health,  aged  twenty-eight,  took  in  mistake  for  Epsom  salt  a  large 
tablespoonful  of  zinc  sulphate.  Violent  vomiting,  with  cramps, 
severe  burning  pain  in  the  stomach,  and  extreme  prostration,  soon 
ensued.  An  hour  later,  the  pulse  was  very  feeble,  small,  and  easily 
compressible,  the  respiration  difficult;  there  was  violent  coughing,  a 
copious  flow  of  tears  from  the  eyes,  and  constant  desire  to  discharge 
the  fseces.  Under  treatment  the  patient  was  soon  convalescent,  but 
experienced  difficulty  of  breathing,  great  prostration,  and  intense  itch- 
ing with  a  sense  of  burning  in  the  skin,  especially  during  the  night, 
for  several  days  afterward.  In  a  case  reported  by  Dr.  Brennan,  a  man 
recovered  after  having  taken  by  mistake  four  ounces  of  this  salt. 

In  poisoning  by  solutions  of  the  chloride  of  zinc,  the  symptoms 
are  much  the  same  as  those  caused  by  the  sulphate.  There  is  an 
immediate  burning  sensation  in  the  throat,  burning  pain  in  the 
stomach,  nausea,  violent  vomiting,  purging,  cold  perspirations,  great 
anxiety,  and  feeble  pulse.     In  some  instances  the  vomited  matters 


404  ZINC. 

are  streaked  with  blood,  owing  to  the  local  action  of  the  poison  upon 
the  throat  and  neighboring  parts. 

In  a  case  of  poisoning  by  Burnett's  disinfecting  fluid,  reported  by 
Dr.  Letheby,  the  patient,  a  child  fifteen  months  old,  was  seized  with 
extreme  prostration,  and  died  in  a  comatose  condition,  ten  hours  after 
taking  the  dose.  In  a  case  communicated  to  Dr.  Taylor,  a  woman, 
aged  twenty-eight  years,  swallowed  an  ounce  of  this  fluid,  and  died 
from  its  effects  four  hours  afterward.  This  is  perhaps  the  most 
rapidly  fatal  case  of  poisoning  by  zinc  yet  recorded.  A  woman, 
forty  years  of  age,  swallowed  a  quantity  of  Burnett's  fluid  in  mis- 
take for  a  glass  of  gin.  It  remained  on  the  stomach  only  about  ten 
minutes,  when  it  was  ejected  by  vomiting.  A  burning  sensation  was 
experienced  in  the  throat  and  chest  for  two  or  three  days ;  this  was 
succeeded  by  an  inability  of  the  stomach  to  retain  food,  and  death 
ensued  at  the  expiration  of  fourteen  weeks,  apparently  from  simple 
prostration,  due  to  want  of  nourishment.  {Amer.  Jour.  Med.  Set., 
Jan.  1860,  190.)  In  an  instance  reported  by  Dr.  Stratton,  of  Mon- 
treal, a  man,  aged  fifty-four  years,  drank  about  a  wineglassful  of  a 
dense  solution  of  chloride  of  zinc,  containing,  as  prepared,  four  hun- 
dred grains  of  the  salt,  and  entirely  recovered  from  its  effects;  not, 
however,  without  experiencing  very  severe  symptoms  for  several  days. 

As  metallic  zinc  is  more  or  less  acted  upon  by  certain  articles  of 
food,  especially  such  as  contain  free  organic  acids  or  fatty  matters, 
its  use  for  culinary  operations  is  not  altogether  free  from  danger. 
In  an  instance  in  which  we  were  consulted,  a  family,  consisting  of 
eight  persons,  suffered  with  symptoms  of  zinc  poisoning,  occasioned 
by  the  use  of  apple-butter  prepared  with  cider  which  had  been  con- 
centrated on  a  galvanized  iron  pan.  On  chemical  examination,  the 
concentrated  cider  was  found  to  contain  1.14  grains  of  zinc  oxide  in 
each  fluid-ounce. 

P.  van  Hamel-Roos  reports  an  instance  [Chem.  News,  May,  1879, 
237)  in  which  seven  persons  were  poisoned  by  using  in  the  prepa- 
ration of  food  enamelled  iron  pans  containing  oxide  of  zinc.  The 
oxide  was  readily  dissolved  from  the  enamel  by  heating  with  highly 
diluted  acetic  acid  and  common  salt. 

Even  ordinary  water  when  kept  in  contact  with  zinc  will,  after  a 
time,  act  upon  the  metal  and  dissolve  it  in  notable  quantity.  This 
action  is  less  likely  to  take  place  with  hard  waters  than  with  rain- 
water. 


POST-MORTEM    APPEARANCES.  405 

Treatment. — This  is  much  the  same  as  in  poisoning  by  salts 
of  lead  and  copper.  No  chemical  antidote  is  known.  The  efforts 
of  the  stomach  should  be  assisted  by  the  free  administration  of  mild 
demulcent  drinks.  The  free  exhibition  of  a  mixture  of  milk  and 
magnesium  hydrate,  and  also  of  decoctions  of  the  vegetable  astrin- 
gents, has  been  recommended.  In  poisoning  by  the  chloride  of 
zinc,  a  solution  of  acid  sodium  carbonate,  followed  by  large  draugiits 
of  any  bland  liquid,  has  been  advised.  Opium  may  be  found  useful 
to  allay  the  subsequent  irritation. 

Post-mortem  Appearances. — In  the  case  already  cited,  in 
which  an  ounce  and  a  half  of  the  sulphate  of  zinc  proved  fatal  in 
thirteen  hours  and  a  half,  the  following  appearances  were  observed, 
forty  hours  after  death  :  great  lividity  of  the  external  surface  of  the 
body;  congestion  of  the  brain  and  its  membranes;  a  congested  state 
of  the  lungs ;  flaccid  condition  of  the  heart,  the  right  cavities  being 
filled  with  black,  thick  blood ;  the  inner  surface  of  the  stomach  was 
covered  with  a  yellowish,  pultaceous  matter,  on  the  removal  of 
which  a  uniform  yellow,  ochreous  color  was  observed,  except  to- 
wards the  great  curvature,  where  it  became  reddish  ;  there  was  also 
a  gelatiniform  softening  of  the  mucous  membrane  of  the  stomach, 
exposing,  in  some  parts,  the  submucous  cellular  tissue.  The  small 
intestines  were  somewhat  injected,  and  contained  yellowish  matters. 
In  another  case  the  stomach  was  very  vascular,  spots  of  ecchymosis 
being  observable,  and  near  the  pylorus  slight  ulceration.  The  brain 
and  its  membranes  were  much  congested,  and  the  pleura  contained  a 
large  quantity  of  sanguinolent  fluid.  {Arne)\  Jour.  3Ied.  Sci.,  July, 
1849,  280.) 

In  a  case  reported  by  Dr.  Ogle,  in  which  the  poison  seems  to 
have  been  taken,  with  suicidal  intent,  in  frequent  doses  for  a  week 
prior  to  death,  the  mucous  surface  from  the  mouth  to  the  stomach 
was  slightly  congested,  and  its  surface  thickened  in  patches,  and  of  a 
grayish-Avhite  color.  The  stomach  was  contracted,  and  the  whole  of 
its  inner  surface  was  of  a  dirty-gray  color,  the  mucous  membrane 
being  very  greatly  thickened,  condensed,  and  indurated,  and  having 
an  appearance  similar  to  that  of  tripe.  The  duodenum  had  the  same 
appearance  in  a  less  degree ;  the  colon  and  rectum  were  contracted, 
but  otherwise  healthy.  There  was  general  congestion  of  the  visceral 
organs,  and  a  dark,  fluid  condition  of  the  blood.  {Lancet,  1859, 
ii.  210.) 


406  ZINC. 

In  a  case  quoted  by  Dr.  A.  Stills  {Mat.  Med.,  ii.  336),  which 
proved  fatal  on  the  fifth  day,  after  a  wineglassful  of  a  concentrated 
solution  of  sulphate  of  zinc  had  been  taken,  the  only  morbid  ap- 
pearances detected  were  patches  of  inflammation  of  the  mucous  mem- 
brane of  the  pyloric  end  of  the  stomach  and  of  the  duodenum. 

In  Dr.  Letheby's  case  of  poisoning  by  Burnett's  disinfecting  fluid, 
before  cited,  twenty-two  hours  after  death,  the  mucous  membrane 
of  the  mouth,  fauces,  and  oesophagus  was  found  of  a  white  color 
and  opaque.  The  stomach  was  hard  and  leathery,  and  contained 
about  an  ounce  and  a  half  of  liquid  resembling  curds  and  whey,  in 
which  chloride  of  zinc  was  afterward  found.  The  inner  surface  of 
the  stomach  had  a  highly  acid  reaction,  was  corrugated,  opaque,  and 
tinged  of  a  dark  leaden  hue;  this  appearance  ceased  abruptly  at  the 
pylorus.  The  lungs  and  kidneys  were  congested.  In  the  case  of 
poisoning  by  this  fluid  in  which  death  did  not  occur  until  the  lapse 
of  fourteen  weeks,  the  stomach  was  found  so  much  contracted  as  to 
contain  only  four  ounces  of  fluid,  and  completely  perforated  in  two 
places  by  ulcers,  one  being  near  the  cardiac  and  the  other  near  the 
pyloric  orifice.  There  was  no  decided  peritonitis,  but  the  whole  of 
the  serous  membrane  had  a  slightly  greasy  feel  when  touched,  as  if 
there  was  some  exudation  on  its  surface. 

Chemical  Properties. 

In  the  Solid  State. — When  a  few  crystals  of  zinc  sulphate, 
placed  in  a  watch-glass,  are  treated  with  a  drop  of  a  solution  of  potas- 
sium chromate,  they  acquire  a  yellow  color,  and  soon  become  con- 
verted into  a  mass  of  small  yellow  granules.  This  reaction,  although 
perhaps  not  entirely  peculiar,  readily  serves  to  distinguish  the  least 
visible  crystal  of  the  zinc  salt  from  magnesium  sulphate,  or  Epsom 
salt,  for  which  it  has  in  several  instances  been  fatally  mistaken,  and 
which,  when  treated  in  a  similar  manner,  slowly  dissolves. 

If  a  small  portion  of  zinc  sulphate  be  heated  on  a  charcoal  sup- 
port in  the  inner  blow-pipe  flame,  it  quickly  fuses  in  its  water  of 
crystallization,  and  leaves  a  residue  which  is  slowly  consumed,  cover- 
ing the  charcoal  in  part  with  a  yellow  incrustation  of  zinc  oxide, 
which  on  cooling  becomes  white.  If  the  unconsumed  residue,  or  the 
incrustation,  be  moistened  with  a  solution  of  cobalt  nitrate,  and  then 
heated  in  the  outer  flame  of  the  blow-pipe,  the  mass  on  cooling 
acquires  a  green  color.     These  reactions  are  peculiar  to  compounds 


SULPHURETTED    HYDROGEN    TEST.  407 

of  /iiic,  and  will  serve  for  the  identification  of  very  minute  quan- 
tities of  the  metal.  It  is  usually  l)est,  however,  before  applying  the 
blow-pipe  heat,  to  mix  the  zinc  compound  with  sodium  carbonate. 

Of  Solutions  of  Zinc. — Pure  aqueous  solutions  of  zinc  sul- 
phate are  colorless,  have  a  styptic  metallic  taste,  and  slightly  redden 
litmus-paper.  When  a  drop  of  the  solution  is  allowed  to  evaporate 
spontaneously,  the  salt  is  left  in  the  form  of  slender  prismatic  crys- 
tals. As  found  in  the  shops,  zinc  sulphate  is  usually  contaminated 
with  iron,  and  sometimes  contains  other  impurities,  which  more  or 
less  modify  its  chemical  reactions. 

In  ascertaining  the  limit  of  thje  reactions  of  the  diflPerent  reagents 
for  zinc,  pure  aqueous  solutions  of  the  sulphate  were  employed.  The 
fractions  indicate  the  fractional  part  of  a  grain  of  oxide  of  zinc,  ZnO, 
or  its  equivalent,  present  in  one  grain  of  the  solution.  The  results, 
unless  otherwise  stated,  refer  to  the  behavior  of  one  grain  of  the 
solution.  One  part  of  the  oxide  corresponds  to  3.54  parts  of  pure 
crystallized  sulphate  of  zinc. 

1.  Sulphuretted  Hydrogen. 

Sulphuretted  hydrogen  gas  throws  down  from  neutral  and  alka- 
line solutions  of  salts  of  zinc  a  white  amorphous  precipitate  of 
hydrated  zinc  sulphide,  ZnS,HoO,  which  is  insoluble  in  the  caustic 
alkalies,  alkaline  sulphides,  and  in  acetic  acid,  but  very  readily  solu- 
ble in  the  stronger  mineral  acids.  In  solutions  containing  either 
free  sulphuric,  hydrochloric,  or  nitric  acid,  the  reagent  fails  to  pro- 
duce a  precipitate.  Even  in  strong  solutions  of  the  normal  salts  of 
these  acids  the  reagent  throws  down  only  a  portion  of  the  zinc ;  but 
from  solutions  containing  only  about  one  per  cent,  or  less  of  these 
salts  the  precipitation  is  complete.  The  se})aration  of  the  precipi- 
tate, especially  from  veiy  dilute  solutions,  is  much  facilitated  by  the 
application  of  a  gentle  heat. 

The  following  results  refer  to  the  behavior  of  ten  grains  of  a 
normal  solution  of  zinc  sulphate. 

1.  1-lOOth  solution  of  zinc  oxide  (  =  37^  grain  ZuO)  yields  an  im- 

mediate precipitate,  and  soon  there  is  a  copious,  white  deposit, 

2.  1-lOOOth  solution:  a  quite  good  precipitate. 

3.  1-1 0,000th  solution :  in  a  very  little  time  the  liquid  becomes  tur- 

bid, and  after  standing  a  few  hours  yields  a  very  satisfactory 
deposit. 


408  ZINC. 

4.  l-25,000th  solution  :    after  a  little  time  the  mixture   becomes 

turbid,  and  after  a  few  hours  there  is  a  quite  distinct  deposit. 

5.  l-50,000th  solution  :  after  a  little  time  the  liquid  becomes  cloudy, 

and  after  about  ten  hours  a  distinct,  flaky  deposit  has  formed. 

The  production  of  a  white  precipitate  by  this  reagent  is  charac- 
teristic of  zinc,  as  this  is  the  only  metal  the  sulphide  of  which  has  a 
white  color.  It  should  be  remembered  that  the  color  of  the  precipi- 
tate may  be  much  modified  by  the  presence  of  even  minute  quantities 
of  other  metals.  It  must  also  be  borne  in  mind  that  solutions  of 
ferric  salts  may  yield  with  sulphuretted  hydrogen  a  white  tur- 
bidity, due  to  the  decomposition  of  the  reagent  with  the  separation 
of  sulphur. 

Ammonium  sulphide  produces  the  same  precipitate  of  zinc  sulphide 
from  neutral  and  allialine  solutions  of  salts  of  the  metal.  In  this 
case  the  precipitation  is  complete,  even  from  concentrated  normal 
solutions  of  any  of  the  salts  of  the  metal.  This  reagent,  however, 
also  produces  in  solutions  of  aluminiuni  a  white  precipitate  of  alu- 
minium  hydrated  sesquioxide,  with  evolution  of  sulphuretted  hydrogen 
gas.  This  precipitate  is  easily  distinguished  from  zinc  sulphide,  in 
being  readily  soluble  in  potassium  hydrate. 

2.  Potassium  Hydrate  and  Ammonia. 

The  fixed  caustic  alkalies  and  ammonia  throw  down  from  normal 
solutions  of  salts  of  zinc,  and  also  from  acid  solutions  when  excess 
of  the  reagent  is  added,  a  white  precipitate  of  zinc  hydroxide,  or 
hydrated  oxide  of  zinc,  ZnOjHgO,  which  is  readily  soluble  in  free 
acids,  and  in  excess  of  the  precipitant.  From  these  alkaline  solutions 
the  whole  of  the  zinc  is  reprecipitated,  as  sulphide,  by  sulphuretted 
hydrogen  gas. 

1.  YTo  grain  of  zinc  oxide,  in  one  grain  of  water,  yields  a  copious, 

gelatinous  precipitate. 

2.  YToo  grain :  a  quite  good,  flocculent  precipitate,  which  readily 

disappears  on  the  addition  of  slight  excess  of  the  reagent. 

3.  Yo",oTo"  grain  yields  with  a  very  minute  quantity  of  the  reagent 

a  slight  turbidity. 
These  reagents  also  produce  white  precipitates  in  solutions  of 
various  other  substances  besides  zinc ;  but  from  these  precipitates 
the  washed  and  dried  zinc  compound  is  readily  distinguished  by  its 
behavior  under  the  blow-pipe  flame,  as  already  pointed  out. 


POTASSIUM   FERRICYANIDE  TEST.  409 

The  alkaline  carbonates  tlirow  down  from  solutions  of  salts  of 
zinc  a  white  ])rcoipitate  of  a  basic  oxycarbonate  of  the  metal,  which 
is  insoluble  in  excess  of  the  fixed  alkaline  carbonates,  but  soluble 
in  excess  of  the  carbonate  and  other  salts  of  ammonium.  The  pre- 
cipitate is  also  readily  soluble  in  acids,  even  acetic  acid,  and  in  the 
caustic  alkalies.  The  limit  of  the  reaction  of  these  reagents  is  the 
same  as  that  of  the  free  alkalies. 

3.  Potassium  Ferroeyanide. 

This  reagent  produces  in  solutions  of  salts  of  zinc  a  white,  amor- 
phous precipitate  of  hydrated  zinc  ferroeyanide,  ZngCygFejSHgO, 
which  is  insoluble  in  acetic,  nitric,  sulphuric,  and  hydrochloric 
acids ;  also  in  ammonia,  in  ammonium  chloride,  and  in  excess  of 
the  precipitant.  In  the  presence  of  excess  of  the  precipitant  the 
precipitate  acquires  a  greenish  or  greenish-blue  color  when  acted 
upon  by  hydrochloric  or  nitric  acid,  due  to  the  decomposition  of 
the  reagent.  Ferroeyanide  of  zinc  is  readily  soluble  in  potassium 
hydrate  to  a  colorless  solution,  from  which  it  is  reprecipitated  by  an 
excess  of  hydrochloric  acid. 

1.  YoT  gr^in  of  zinc  oxide,  in  one  grain  of  water,  yields  a  very 

copious,  gelatinous  precipitate. 

2.  YoViT  grain  :  a  quite  good,  flocculent  deposit. 

3.  TTT.Wo  gi'ain :    in  a  very  little  time  the  mixture  becomes   quite 

turbid. 

4.  2T.V0T  grain  :  after  a  few  minutes  a  very  perceptible  turbidity. 
This   reagent   also  produces  white  precipitates  in  solutions  of 

several  other  metals.     Most  of  these  precipitates,  however,  unlike 
that  from  zinc,  are  readily  soluble  in  hydrochloric  acid. 

4.  Potassium  Ferricyanide. 

This  reagent  occasions  in  solutions  of  salts  of  zinc  a  yellow, 
reddish-brown,  or  greenish,  amorphous  precipitate,  the  color  depend- 
ing upon  the  strength  of  the  solution,  and  also,  somewhat,  upon  the 
relative  quantity  of  the  reagent  present.  The  precipitate  is  insolu- 
ble in  acetic,  hydrochloric,  sulphuric,  and  nitric  acids,  but  is  readily 
soluble  to  a  clear  solution  in  potassium  hydrate,  from  which  it 
is  reprecipitated  by  hydrochloric  and  sulphuric  acids.  It  is  also 
soluble  in  ammonia,  but  in  a  very  little  time  the  solution  becomes 
turbid;  from  this  solution  it  is  also  reprecipitated  by  acids. 


410  ZINC. 

1.  YST  gJ'^i'^  of  zioc  oxide  yields  a  copious,  dirty -yellow  precipitate, 

which  very  soon  assumes  a  brownish  color. 

2.  y^Q-g-  grain  :  a  good,  greenish-yellow  deposit. 

3.  YF.wo  grain  '■  3-  very  fair,  greenish  turbidity,  and  very  soon  a 

flocculent  precipitate. 

4.  2T,ToT  g^'ain  :   the  mixture  very  soon  becomes  turbid,  and  in  a 

little  time  yields  perceptible  flakes. 
The  reaction  of  this  reagent  is  common  to  solutions  of  several 
different  metals. 

5.   Oxalic  Acid. 

Oxalic  acid  throws  down  from  solutions  of  salts  of  zinc  a  white, 
granular  or  crystalline  precipitate  of  zinc  oxalate,  ZnC204,2Aq, 
which  is  insoluble  in  acetic  acid,  but  readily  soluble  in  the  stronger 
mineral  acids ;  it  is  also  soluble  in  caustic  ammonia,  but  almost  in- 
soluble in  ammonium  chloride.  The  separation  of  the  precipitate  is 
much  facilitated  by  a  gentle  heat ;  also  by  agitation  of  the  mixture. 

1.  Y^  grain   of  zinc  oxide,  in  one  grain  of  water,  yields  an  im- 

mediate turbidity,  and  in  a  little  time  a  copious  granular  pre- 
cipitate. 

2.  y-^oT  grain :  in  a   little   time  a  distinct  precipitate,   and    soon  a 

quite  good  deposit  of  granules  and  octahedral  crystals,  Plate 
V.,fig._6. 

3.  ^Q^QQ  grain :  after  several  minutes  small  granules  form  along  the 

margin  of  the  drop,  and  in  ten  or  fifteen  minutes  there  is  a  very 

satisfactory  granular  and  octahedral  deposit. 
Oxalic  acid  throws  down  white  precipitates  from  solutions  of 
salts  of  most  of  the  metals,  and  in  the  case  of  calcium,  and  also  of 
strontium,  the  precipitate  may  have  the  same  microscopic  characters 
as  the  oxalate  of  zinc.  The  true  nature  of  the  zinc  precipitate, 
however,  may  be  readily  determined  by  its  behavior  before  the 
blow-pipe. 

6.  Potassium  Chr ornate. 

Normal  potassium  chromate  produces  in  solutions  of  zinc  sul- 
phate a  bright  yellow,  amorphous  precipitate,  which,  according  to 
Thomson,  consists  of  the  subchromate  of  zinc.  At  ordinary  tem- 
peratures the  precipitate  is  somewhat  slow  to  form,  even  from  strong 
solutions,  but  it  separates  immediately  on  the  application  of  heat. 


SODIUM    PHOSrHATK   TRST.  411 

It  is  insoluble  in  excess  of  the  precipitant,  but  readily  soluble  in 
acetic  acid,  and  in  ammonia. 

1.  ^  grain  of  zinc  oxide  yields,  in  the  cold,  an   immediate  cloudi- 

ness, and  soon  a  copious,  yellow  precipitate. 

2.  ^^\^  grain  :   an  immediate  turbidity,  and  soon  a  <rood,  flocculent 

deposit. 

3.  ^^^Viro   gJ'a'"  =    ^^^^^   '*    ''"^^'   *'"^^   *'*^    mixture    becomes   quite 

turbid. 
This  reagent  produces  similar  yellow  precipitates   in  solutions 

of  several  other  metals. 

Potassmm  dichromate  fails  to  produce  a  precipitate,  even  in  con- 
centrated normal  solutions  of  salts  of  zinc. 

7.  Sodium  Phosphate. 
Ordinary  sodium  phosphate  throws  down  from  solutions  of  salts 
of  zinc  a  white  precipitate  of  tribasic  zinc  phosphate,  Zn32P04,  which 
is  soluble  in  acids,  even  in  acetic  acid,  also  in  caustic  potash  and  in 
ammonia,  but  only  sparingly  soluble  in  ammonium  chloride.  From 
strong  solutions  the  precipitate  as  first  produced  is  gelatinous,  whilst 
from' dilute  solutions  it  is  flocculent;  but  after  standing  some  time 
it  diminishes  in  volume  and  becomes  converted,  at  least  partially, 
into  crystalline  plates:  this  change  is  produced  immediately  or  in  a 
very  little  time  by  boiling  the  mixture. 
1    _i      o-rain  of  zinc  oxide  yields  a  quite  copious  gelatinous  pre- 

*  10  0     & 

cipitate. 

2.  ^-^  graiu  :  a  good,  flocculent  deposit. 

3.  -^^j^  grain  :  after  some  minutes  a  quite  distinct  turbidity. 

*  The' production  of  a  white  precipitate  by  this  reagent  is  common 
to  solutions  of  quite  a  number  of  the  metals. 

Detection  of  the  Acid.— The  tests  now  considered  would, 
of  course,  serve  only  for  the  detection  of  the  base  of  the  zinc  salt. 
The  presence  of  sulphuric  acid,  when  combined  with  the  metal,  may 
be  readily  detected  by  acidulating  the  solution  with  nitric  acid  and 
treating  it  with  barium  chloride,  by  which  the  sulphuric  acid  will 
be  precipitated  as  white  barium  sulphate,  which  is  insoluble  in  nitric 
acid.  The  presence  of  chlorine  or  hydrochloric  acid  may  be  deter- 
mined by  treating  the  solution,  acidulated  witii  nitric  acid,  with  silver 
nitrate,  when  any  chlorine  present  will  be  thrown  down  as  silver 


412 


ZINC. 


chloride,  which  is  readily  soluble  in  ammonia,  but  insoluble  in  diluted 
nitric  acid. 

Separation  from  Organic  Mixtures. 

Contents  of  the  Stomach. — The  same  method  of  analysis  is  equally 
applicable  for  the  examination  of  suspected  articles  of  food,  vomited 
matters,  and  the  contents  of  the  stomach.  Salts  of  zinc  are  more 
or  less  decomposed  and  precipitated  by  albumen,  fibrin,  casein,  and 
certain  other  organic  principles.  When,  therefore,  the  suspected 
mixture  contains  any  solid  matter,  the  whole,  after  the  addition  of 
water  if  thought  best,  should  be  acidulated  with  acetic  acid  and 
gently  heated  for  some  time,  when  any  organic  precipitate  of  zinc 
present  will  be  dissolved.  The  solution  thus  obtained  is  filtered, 
and  the  filtrate,  after  concentration  if  necessary,  treated  with  ammo- 
nium sulphide  as  long  as  a  precipitate  is  produced,  after  which  it  is 
gently  warmed,  to  facilitate  the  complete  separation  of  the  precipitate. 
The  precipitate  is  then  collected  on  a  filter,  washed,  and  while  still 
moist  digested  with  nitric  acid,  in  which  the  zinc  will  dissolve,  form- 
ing nitrate  of  the  metal ;  at  the  same  time,  any  iron  present  will  be 
oxidized  and  dissolved  as  ferric  nitrate.  The  solution  is  now  evapo- 
rated to  dryness,  to  expel  the  excess  of  acid,  the  residue  dissolved  in 
a  small  quantity  of  distilled  water,  and  the  filtered  liquid  examined 
by  the  ordinary  tests  for  zinc. 

Should  the  solution  contain  iron,  which  is  a  frequent  impurity  in 
salts  of  zinc,  the  chemical  reactions  of  the  latter,  as  already  pointed 
out,  will  be  more  or  less  modified.  These  metals  may  be  separated 
by  the  addition  of  excess  of  caustic  ammonia,  which  will  precipitate 
the  iron  as  hydrated  sesquioxide,  while  the  zinc  will  be  redissolved 
and  remain  in  solution.  Should  the  iron  exist  as  a  ferrous  salt, 
before  precipitating  with  ammonia  it  must  be  converted  into  a  ferric 
salt,  by  boiling  the  mixture  with  a  little  nitric  acid.  After  separating 
the  precipitated  iron  oxide  by  a  filter,  the  zinc  in  the  ammoniacal 
filtrate  may  be  precipitated  as  sulphide  by  sulphuretted  hydrogen; 
or,  the  solution  may  be  exactly  neutralized  with  acetic  acid,  and  then 
tested  in  the  ordinary  manner.  As  this  neutralization  would  give 
rise  to  an  ammonium  salt,  in  which  the  precipitates  produced  by 
many  of  the  reagents  for  zinc  are  more  or  less  soluble,  if  only  a 
minute  quantity  of  the  metal  be  present,  it  is  best  to  expel  the  excess 
of  ammonia,  by  evaporating  the  solution  to  dryness,  and  then  redis- 


QUANTITATIVE   ANALYSIS.  413 

solve  the  residue  in  a  small  quantity  of  water  containing  a  drop  or 
two  of  acetic  acid. 

From  the  Tissues. — Absorbed  zinc  may  be  recovered  by  boiling 
the  finely  divided  tissue  with  nitric  acid  diluted  with  five  or  six 
volumes  of  water,  until  the  orj^aiiic  matter  is  completely  disintegrated. 
The  mass  is  then  transferred  to  a  muslin  strainer,  the  strained  liquid 
evaporated  to  dryness,  and  the  residue  moistened  with  pure  nitric 
acid,  and  heated  until  the  organic  matter  is  entirely  charred.  The 
dry  mass  thus  obtained  is  treated  with  water  containing  a  little 
hydrochloric  acid,  the  filtered  liquid  evaporated  to  dryness  on  a 
water-bath,  the  residue  dissolved  in  pure  water,  and  the  solution 
treated  with  ammonium  sulphide.  Any  precipitate  thus  obtained  is 
collected,  washed,  and  examined  in  the  manner  before  described. 

In  several  instances  of  poisoning  by  the  salts  of  zinc,  the  metal 
was  readily  discovered  in  the  blood  and  tissues  after  death,  even  in 
some  cases  after  comparatively  long  periods.  It  need  hardly  be  re- 
marked that  when  the  metal  is  found  in  its  absorbed  state  it  will  be 
impossible  from  chemistry  alone  to  determine  in  what  form  it  was 
originally  taken. 

Quantitative  Analysis. — Zinc  is  usually  estimated  in  the 
form  of  oxide  of  the  metal.  For  this  purpose  the  solution  is  heated 
to  about  the  boiling  temperature,  and  treated  with  a  somewhat  dilute 
solution  of  sodium  carbonate  as  long  as  a  precipitate  is  produced, 
after  which  it  is  boiled  for  some  minutes.  Tiie  precipitate  is  then 
allowed  to  subside,  collected  on  a  filter,  w^ashed  with  hot  water,  dried, 
and  ignited.  The  whole  of  the  zinc  will  now  exist  in  the  form  of 
monoxide,  one  hundred  parts  of  which  correspond  to  354.13  parts  of 
pure  crystallized  sulphate,  or  167.77  parts  of  anhydrous  chluride  of 
zinc. 


PART  SECOND. 

VEGETABLE  POISONS. 


VEGETABLE  POISONS. 


INTEODUCTIOlSr. 

NATURE   OF   VEGETABLE    POISONS— GENERAL   METHODS    FOR   RECOVERING 
THE   ALKALOIDS   FROM   ORGANIC   MIXTURES. 

The  different  poisonous  plants  owe  their  toxic  properties  to  the 
presence  of  one  or  more  proximate  principles,  some  of  which  have 
not  as  yet  been  obtained  in  their  isolated  state.  Most  of  these  active 
principles  have  basic  properties,  and  such,  as  a  class,  from  their  gen- 
eral chemical  resemblance  to  the  ordinary  alkalies,  have  been  named 
ALKALOIDS,  or  VEGETABLE  ALKALIES.  A  few  othecs,  in  regard  to 
their  chemical  nature,  are  neutral;  while  others  still  have  acid  prop- 
erties. In  poisoning  by  these  substances,  the  poison  is  usually  taken 
in  its  more  or  less  crude  state;  but  in  some  instances,  as  in  the  case 
of  strychnine  and  morphine,  it  is  frequently  taken  in  its  pure  form. 
The  present  consideration  of  this  class  of  poisons  will  be  confined  to 
such  as  contain  principles  the  nature  of  which,  even  when  present 
only  in  minute  quantity,  can  be  fully  established. 

The  natural  alkaloids  always  exist  in  the  plants  from  which  they 
are  obtained  in  the  form  of  salts,  which  generally  contain  an  organic 
acid  peculiar  to  the  plant  in  which  the  base  is  found.  They  all  con- 
tain nitrogen,  usually  in  the  proportion  of  one  atom,  but  sometimes 
two  atoms,  combined  with  various  proportions  of  carbon  and  hydro- 
gen, sometimes  alone,  but  generally  with  the  addition  of  oxygen. 
They  are  naturally  divided  into  two  classes :  the  volatile  or  liquid, 
and  the  fixed  alkaloids. 

The  volatile  alkaloids  consist  of  carbon,  hydrogen,  and  nitrogen ; 
are  liquid  at  ordinary  temperatures;  have  a  strong  and  peculiar  odor  ; 
and  pass  over  with  the  vapor  of  water  when  their  free  aqueous  solu- 

27  -il" 


418  VEGETABLE   POISONS:    INTRODUCTION. 

tions  are  distilled.  On  the  other  hand,  the  fixed  alkaloids  contain 
carbon,  hydrogen,  nitrogen,  and  oxygen ;  are  solid  at  ordinary  tem- 
peratures; destitute  of  odor;  and  do  not  distil  with  the  vapor  of 
water.  In  their  free  state  most  of  the  alkaloids  are  but  sparingly 
soluble  in  water,  but  readily  soluble  in  alcohol,  ether,  and  chloro- 
form. Their  salts  are,  for  the  most  part,  soluble  in  water  and  in 
alcohol,  but  insoluble  in  ether  and  in  chloroform. 

In  their  pure  state  many  of  these  substances  may  be  identified 
with  as  much  certainty,  and  in  as  minute  quantity,  as  most  of  the 
inorganic  poisons ;  but  their  detection  when  present  in  complex 
mixtures  is  generally  much  more  difficult,  requiring  more  care  and 
delicacy  of  manipulation,  and  is  attended  with  much  greater  loss  of 
material  than  the  recovery  of  inorganic  substances.  Again,  as  the 
quantity  of  the  alkaloids  necessary  to  prove  fatal  is  usually  very 
much  less  than  that  of  inorganic  poisons,  the  actual  quantity  of 
poison  present  in  death  from  the  former  is  generally  much  less  than 
that  in  poisoning  by  the  latter.  Moreover,  since  all  organic  poisons 
sooner  or  later  undergo  complete  decomposition  in  the  dead  body, 
they  can  at  most  be  detected  after  only  very  limited  periods,  at  least 
in  comparison  with  some  of  the  metallic  poisons. 

From  these  considerations  it  is  obvious  that  in  poisoning  by  these 
substances  it  may  often  happen  that  there  will  be  a  failure  to  detect 
the  poison.  Even  when  the  poison  is  discovered,  the  amount  recov- 
ered is  frequently  so  minute  as  to  render  it  impossible  to  make  a  quan- 
titative analysis.  In  many  instances  the  nearest  approach  that  can 
be  made  as  to  the  quantity  recovered  is  by  observing  the  intensity  of 
the  reactions  of  the  reagents  applied,  and  comparing  these  with  the 
reactions  of  known  quantities  of  the  poison. 

For  the  recovery  and  purification  of  the  alkaloids,  when  mixed 
with  foreign  organic  matters,  several  general  methods  have  been  pro- 
posed ;  but,  as  might  be  expected,  these  processes  are  not  equally  ap- 
plicable for  all  the  members  of  this  class  of  poisons.  Some  of  these 
methods — most  of  which  are  based  upon  the  principles  first  pointed 
out  in  1851  by  M.  Stas,  of  Brussels — will  now  be  described,  with 
some  comments  on  each. 

1.  Method  of  Stas. 

This  method  is  much  the  same  as  that  usually  employed  for  ex- 
tracting the  alkaloids  from  the  vegetables  in  which  they  occur.     It 


RECOVERY    15 Y    METHOD   OF   8TAS.  419 

takes  :ulv:iiit:ii2:('  of  the  fact  that  tlu!  acid  salts  of  the  alkaloids  are 
solnhic  in  water  and  in  alcohol;  and  that  when  a  solution  of  this 
kind  is  decomposed  by  the  addition  of  an  excess  of  a  fixed  mineral 
alkali  or  its  carbonate  and  aj^itated  with  pure  Ether,  this  liquid  will 
dissolve  the  liberated  alkaloid.  In  the  case  of  the  volatile  alkaloids, 
advantaire  is  also  taken  of  the  insolul)ilit}M)f  their  acid  salts  in  ether 
to  sej)arate  such  organic  impurities  as  are  soluble  in  this  liquid,  by 
agitating  the  mixture  with  the  fluid  while  the  alkaloid  is  in  the  forna 
of  a  salt. 

To  apply  this  method,  the  suspected  mixture,  such  as  the  contents 
of  the  stomach,  is  treated  with  about  twice  its  weight  of  pure  concen- 
trated alcohol,  then  distinctly  acidulated  with  tartaric  or  oxalic  acid, 
and  the  whole  heated  in  a  flask  to  about  71°  C.  (160°  F.).  If 
the  substance  under  examination  is  one  of  the  solid  organs  of  the 
body,  as  the  liver,  heart,  or  lungs,  it  is  first  cut  into  very  small  frag- 
ments and  the  mass  moistened  with  strong  alcohol,  then  strongly 
pressed,  and  the  operation  repeated  with  fresh  portions  of  alcohol 
until  the  soluble  matters  are  entirely  extracted ;  the  mixed  alcoholic 
fluids  are  then  acidified  with  tartaric  or  oxalic  acid,  and  heated  in 
the  manner  just  described. 

When  the  alcoholic  mixture  has  entirely  cooled,'the  fluid  is  fil- 
tered, the  solids  on  the  filter  well  washed  with  strong  alcohol,  and 
the  mixed  filtrates  evaporated  to  near  dryness  at  a  temperature  not 
exceeding  35°  C.  (95°  F.),  either  in  a  strong  current  of  air  or  in 
vacuo  over  sulphuric  acid.  If,  during  the  evaporation,  fatty  or  other 
insoluble  matters  separate,  the  concentrated  fluid  is  filtered,  the  filter 
washed  with  alcohol,  and  the  filtrate  and  washings  evaporated  as 
above,  at  a  temperature  not  exceeding  35°  C.  The  residue  is  then 
digested  with  cold  absolute  alcohol,  the  mixture  filtered,  the  filter 
washed  with  alcohol,  and  the  mixed  liquids  evaporated  at  a  low  tem- 
perature to  dryness.  The  residue  thus  obtained  is  dissolved  in  a 
very  small  quantity  of  water,  and  the  solution  treated  with  slight 
excess  of  powdered  acid  sodium  carbonate.  The  solution  is  now 
violently  agitated  in  a  stout  test-tube  or  a  small  flask,  with  four  or 
five  volumes  of  pure  Ether,  the  mixture  allowed  to  repose,  and  then 
a  small  portion  of  the  clear  supernatant  ether  transferred  to  a  watch- 
glass  and  allowed  to  evaporate  spontaneously. 

If  the  transferred  ether  contained  a  liquid  alkaloid  in  not  too 
minute    quantity,  it  will    now  remain    in  the  watch-glass  as  oily 


420  VEGETABLE   POISONS:    INTRODUCTION". 

Streaks,  which,  upon  the  application  of  a  very  gentle  heat,  collect 
into  a  drop  and  emit  the  peculiar  pungent  odor  of  the  alkaloid 
(nicotine  or  conine),  more  or  less  masked  by  that  of  any  animal 
matter  present.  If,  however,  a  fixed  alkaloid  be  present,  there  will 
be  traces  of  a  solid  residue,  destitute  of  any  odor  other  than  that  of 
animal  matter. 

The  alkaloid  is  liquid  and  volatile. — If  traces  of  a  volatile  alka- 
loid are  thus  discovered,  the  contents  of  the  vessel  from  which  the 
small  portion  of  ether  was  taken  are  rendered  distinctly  alkaline, 
and  the  whole  violently  agitated ;  after  repose,  the  clear  ether  is 
separated  by  means  of  a  pipette,  and  the  residue  washed  in  a  similar 
manner  three  or  four  times  with  fresh  portions  of  ether.  The  mixed 
ethereal  liquids  are  now  agitated  with  a  small  quantity  of  water  con- 
taining sufficient  diluted  sulphuric  acid  to  render  the  whole  distinctly 
acid ;  the  ether  is  then  decanted,  and  the  aqueous  solution  washed 
two  or  three  times  with  fresh  portions  of  ether. 

By  this  treatment  the  aqueous  solution  will  retain,  in  the  form  of 
sulphate,  any  volatile  alkaloid  present ;  while  the  decanted  ether  will 
remove  such  foreign  matters  as  are  soluble  in  that  liquid.  As,  how- 
ever, the  sulphate  of  conine  is  not  altogether  insoluble  in  ether,  this 
fluid  may  contain  a  small  quantity  of  that  salt. 

The  aqueous  solution  is  now  mixed  with  an  excess  of  potassium 
or  sodium  hydrate,  and  again  agitated  with  three  or  four  volumes  of 
pure  ether,  which  will  dissolve  the  liberated  alkaloid,  and  also  any 
ammonia  present.  The  ether  is  then  carefully  decanted,  the  residue 
washed  with  a  fresh  portion  of  ether,  the  mixed  ethers  exposed  to 
spontaneous  evaporation  at  a  low  temperature,  and  the  last  trace  of 
ammonia,  if  present,  removed  by  placing  the  dish  containing  the 
residue  for  a  few  moments  in  vacuo  over  strong  sulphuric  acid,  when 
the  alkaloid  will  be  left  in  its  pure  state.  The  exact  nature  of  the 
alkaloid  is  then  determined  by  appropriate  tests. 

The  alkaloid  is  solid  and  fixed. — If  the  evaporation  of  the  small 
portion  of  ether,  taken  from  the  mixture  neutralized  by  acid  sodium 
carbonate,  does  not  indicate  the  presence  of  a  volatile  alkaloid,  the 
original  mixture  is  treated  with  excess  of  a  fixed  alkali,  and  again 
violently  agitated ;  when  the  liquids  have  separated,  the  clear  ether 
is  decanted,  the  residue  thoroughly  extracted  with  fresh  portions  of 
ether,  and  the  united  ethereal  liquids  allowed  to  evaporate  sponta- 
neously at  a  low  temperature.     The  residue  thus  obtained  is  some- 


RECOVERY    BY    METHOD    OF   KTAS.  121 

times  in  tlio  solid  form,  l)ut  more  frequently  is  ;i  colorless  milky 
liquid,  in  which  are  suspended  small  solid  particles.  It  has  usually 
a  distinct  alkaline  reaction,  and  an  offensive  animal  odor,  which, 
however,  is  not  pungent. 

The  residue  is  now  treated  with  a  few  drops  of  alcohol,  and  the 
liquid  allowed  to  evapotate  spontaneously.     If  this  fails  to  furnish 
the  alkaloid  in  its  crystalline  form,  a  few  drops  of  water  feebly  acid- 
ulated with  suliduiric  acid  are  added  and  gently  rotated  over  the 
residue.     This  will  convert  the  alkaloid  into  a  sulphate  of  the  base, 
which  will  dissolve;  while  any  fatty  matters  present  will   usually 
remain  undissolved  and  adhere  to  the  sides  of  the  dish.     The  liquid 
is  cautiously  decanted  or  filtered,  the  residue  washed  with  a  few  drops 
of  acidulated  water,  and  the  mixed  liquids  evaporated  to  a  small 
volume  in  vacuo,  or  under  a  receiver  over  strong  sulphuric  acid. 
The  concentrated  liquid  is  then  rendered  alkaline  by  a  concentrated 
solution  of  potassium  or  sodium  carbonate,  and  the  mixture  treated 
with  absolute  alcohol,  which  will   dissolve- the  liberated   alkaloid, 
while  the  alkali  sulphate  formed,  together  with  any  excess  of  alkali 
carbonate  present,  will  remain  undissolved.     The  alcoholic  solution 
is  carefully  decanted  or  filtered,  and  exposed  to  spontaneous  evap- 
oration, when  the  alkaloid  will  be  left  in  its  pure  state.     Its  true 
nature  is  now  determined  by  the  appropriate  reagents. 

On  applying  the  principles  now  described,  M.  Stas  succeeded 
in  isolating,  when  previously  mixed  with  foreign  organic  matters,  a 
great  number  of  the  alkaloids.  And  he  also  thus  extracted  mor- 
phine from  opium;  strychnine  and  brucine  from  nux  vomica;  vera- 
trine  from  extract  of  veratrum  ;  emetine  from  extract  of  ipecacuanha; 
colchicine  from  tincture  of  colchicum ;  aconitine  from  an  aqueous 
extract  of  aconite  ;  hyoscyamine  from  an  old  extract  of  henbane;  and 
atropine  from  an  old  tincture  of  belladonna.  {Bulletin  de  V Academie 
de  Medeeine  de  Belgique,  vi.  304.) 

In  applying  the  above  method,  the  operator  should  bear  in  mind 
that  the  different  alkaloids  differ  greatly  in  regard  to  their  solubility 
in  ether,  and,  therefore,  that  the  quantity  of  this  fluid  necessary  for 
their  complete  extraction  from  aqueous  or  alkaline  mixtures  will 
vary,  other  things  being  equal,  with  the  nature  of  the  base.  In  all 
cases,  the  quantity  of  a  given  substance  that  ether  or  any  similar 
liquid  will  separate  from  its  aqueous  or  alkaline  solution — the  quan- 


422  VEGETABLE   POISONS:    INTRODUCTION. 

titles  of  the  difiPerent  liquids  being  equal — will  be  in  the  same  ratio 
as  the  solubility  of  the  substance  in  the  former  menstruum  exceeds 
its  solubility  in  the  latter. 

For  the  extraction  of  most  of  the  vegetable  bases  considered  in 
the  present  treatise  the  method  of  Stas  is  very  applicable ;  but  for 
others  it  is  only  partially  successful,  or  entirely  fails,  especially  when 
the  alkaloid  is  present  in  very  complex  mixtures.  Thus,  solanine 
requires  something  over  six  thousand  times  its  weight  of  ether  for 
solution,  and  therefore  the  quantity  of  this  liquid  necessary  for  the 
extraction  of  even  a  small  quantity  of  the  alkaloid  is  so  great  that 
it  at  the  same  time  dissolves  so  much  foreign  matter  as  to  render  the 
ethereal  residue  unfit  for  the  application  of  special  tests.  The  same 
difficulty  is  also  experienced  in  the  separation  of  morphine,  which  in 
its  crystalline  state  requires  nearly  eight  thousand  times  its  weight 
of  ether  for  solution,  and  is  at  the  same  time  somewhat  soluble  in 
alkaline  fluids.  This  difficulty  is  removed  to  a  considerable  extent, 
as  first  suggested  by  Poellnitz,  by  quickly  agitating  the  aqueous  al- 
kaline solution  with  ether  and  decanting  this  fluid  before  the  mor- 
phine assumes  the  crystalline  form.  Again,  in  the  case  of  nicotine, 
large  quantities  and  repeated  agitations  with  ether  are  required  for 
its  complete  separation  from  aqueous  solutions ;  since,  although  the 
alkaloid  is  very  soluble  in  ether,  yet  it  is  also  freely  soluble  in  water. 
In  the  special  consideration  of  the  different  alkaloids,  their  exact 
solubility  in  water  and  ether,  as  well  as  in  chloroform,  will  be  pointed 
out. 

In  the  application  of  the  above  method  for  the  detection  of  the 
fixed  alkaloids.  Prof.  Otto  strongly  advises  [Detection  of  Poisons, 
160)  to  pursue  much  the  same  course  as  that  advised  for  the  recovery 
of  the  volatile  or  liquid  bases.  Thus,  the  organic  mixture  is  treated 
with  strong  alcohol  and  oxalic  or  tartaric  acid,  and  the  whole  gently 
heated;  the  cooled  liquid  is  then  filtered,  the  filtrate  concentrated, 
the  liquid  again  filtered,  then  evaporated  to  dryness,  the  residue 
extracted  with  absolute  alcohol,  the  filtered  extract  evaporated  to 
dryness,  and  the  dry  residue  dissolved  in  a  small  quantity  of  water. 
All  these  operations  are  conducted  in  the  same  manner  as  before 
described. 

Instead  of  now  treating  the  aqueous  solution — which  contains 
the  alkaloid  in  the  form  of  a  salt — with  acid  sodium  carbonate  or 
the  caustic  alkali,  it  is  agitated  with  pure  ether,  and  the  operation 


RECOVERY    HY    MiyniOl)    OF    UODGERS   AND   QIRDWOOD. 


423 


repeated  as  lon^r  as  tliis  liquid  extracts  any  coloring  matter;  it  is 
then  tivat.'tl  with  excess  of  a  mineral  alkali,  and  again  agitated  with 
ether,  which  will  now  dissolve  the  liberated  alkaloid,  and  leave  it, 
upon'spontaneous  evaporation,  in  its  nearly  or  altogether  pure  state, 
and  not  unfrequently  in  the  crystalline  form. 

Rei)eated  experiments  in  our  own  hands  with  several  of  the  fixed 
alkaloids  have  fully  confirmed  the  advantages  claimed  by  Prof.  Otto 
for  this  process,  kven  granting  that  the  ether  takes  up  a  trace  of 
the  alkaloidal  salt,  still,  he  remarks,  this  method  deserves  the  prefer- 
ence, since  a  small  quantity  of  the  alkaloid  in  a  pure  state  is  infi- 
nitely more  valuable  for  our  purpose  than  a  larger  quantity  in  a  state 
of  impurity. 

2.  Method  of  Rodgers  and  Girdwood. 
This  process  was  recommended  by  its  authors  [Lancet,  June, 
1856,  718)  simply  for  the  recovery  of  strychnine,  but,  with  slight 
modifications,  it  is  equally  applicable  for  the  detection  of  most  of  the 
alkaloids.  In  principle  it  is  much  the  same  as  the  method  of  Stas, 
only  that  Chloroform  instead  of  ether  is  used  as  the  solvent  of 
the  liberated  alkaloid.     The  details  of  this  method  are  as  follows : 

The  organic  mixture,  as  the  contents  of  the  stomach,  is  treated 
with  water  acidulated  with  hydrochloric  acid,  and  digested  at  a 
moderate  heat  for  about  two  hours ;  when  the  mass  has  cooled,  the 
liquid  is  separated  by  means  of  a  muslin  strainer,  then  filtered,  and 
evaporated  to  dryness  over  a  water-bath.  The  residue  thus  obtained 
is  digested  with  strong  alcohol  containing  a  few  drops  of  hydro- 
chlorTc  acid,  the  solution  filtered,  evaporated  to  dryness,^  and  the 
residue  extracted  with  distilled  water.  This  aqueous  solution  is  fil- 
tered, the  filtrate  supersaturated  with  ammonia,  and  the  mixture 
agitated  with  about  its  own  volume  of  chloroform.  When  the  chloro- 
form has  completely  subsided,  it  is  transferred,  by  means  of  a  pipette, 
to  a  small  evaporating-dish,  and  evaporated  to  dryness.  This  residue 
contains  any  strychnine  present,  together  with  more  or  less  foreign 
organic  matter.  To  destroy  the  latter,  the  residue  is  moistened  with 
concentrated  sulphuric  acid  and  allowed  to  remain  over  a  water-bath 
for  at  least  half  an  hour ;  the  mixture  is  then  treated  with  pure  water, 
the  filtered  liquid  rendered  slightly  alkaline  with  ammonia,  and  the 
alkaloid  again  extracted  with  chloroform. 

The  chloroform  solution  thus  obtained  usually  contains  the  strych- 


424  VEGETABLE   POISONS:    rNTEODUCTIO]sr. 

nine  in  a  sufficiently  pure  state  for  special  testing.  If,  however, 
a  small  portion  of  the  liquid  upon  evaporation  leaves 'a  residue, 
which  when  moistened  with  concentrated  sulphuric  acid  becomes 
charred,  the  whole  of  the  chloroform  is  evaporated  to  dryness,  and 
'the  residue  again  charred  with  sulphuric  acid,  in  the  manner  just 
described,  the  alkaloid  being  again  extracted  from  the  alkaline  liquid 
by  chloroform. 

A  small  portion  of  the  separated  chloroform  is  now  allowed  to 
evaporate  drop  by  drop  within  as  small  a  space  as  possible,  in  a 
white  porcelain  capsule.  The  residue  thus  obtained  is  tested  in  the 
ordinary  manner. 

In  case  the  liver,  spleen,  or  kidneys  are  the  subject  of  analysis, 
the  solid  organ  should  be  reduced  to  a  pulp  in  a  mortar  previous  to 
digestion  in  acidulated  water.  In  the  case  of  the  tissues,  if  recent, 
they  should  be  cut  into  very  small  pieces,  and  triturated  in  a  similar 
manner. 

As  most  of  the  alkaloids  are  much  more  freely  soluble  in  chloro- 
form than  in  ether,  the  former  of  these  liquids  is  much  better  adapted 
than  the  latter  for  the  separation  of  these  poisons  from  organic  mix- 
tures. 

3.  ]\Iethod  of  Uslae  axd  Eedmax^'. 

This  process  is  founded  on  the  fact  that  the  free  alkaloids  are 
quite  freely  soluble  in  pure  Amyl  Alcohol  ;  while,  on  the  other 
hand,  their  hydrochlorides  are  insoluble  in  this  menstruum,  and 
therefore  the  former  are  readily  removed  from  their  solution  in  this 
liquid  by  shaking  the  mixture  with  water  acidulated  with  hydrochlo- 
ric acid.    The  maniptilations  according  to  this  method  are  as  follows : 

The  suspected  mixture,  made  if  necessary  into  a  thin  paste  with 
water,  is  slightly  acidulated  with  liydrochloric  acid,  and  digested  for 
one  or  two  hours  at  a  temperature  of  about  70°  C.  (158°  F.).  It  is 
then  transferred  to  a  linen  cloth  which  has  been  previously  moistened 
with  water,  and  when  the  liquid  has  passed,  the  residue  is  exhausted 
with  hot  water  acidulated  with  hydrochloric  acid,  and  the  combined 
liquids  treated  with  slight  excess  of  ammonia,  after  which  they  are 
concentrated,  first  over  a  direct  flame,  then  evaporated  to  dryness 
on  a  water-bath.  The  residue  thus  obtained  is  extracted  three  or 
four  times  with  hot  amyl  alcohol,  and  the  united  solutions  filtered 
through  paper,  previously  moistened  with  the  alcohol.     The  fihrate 


RECXJVERY    BY    METHOD    OF    ISLAU    AND    ERDMANN. 


425 


has  usually  a  yellow  color,  and  contains,  besides  the  alkaloid,  ftitty 
and  coloring  matters.  To  free  it  from  the  latter,  the  liquid  is  trans- 
ferred to  a  cylindrical  vessel,  and  violently  agitated  with  several 
times  its  volume  of  nearly  boilin.tr  water,  acidulated  with  hydro- 
chloric acid.  By  this  operation  the  alkaloid  is  removed  from  its 
alcoholic  solution,  being  taken  up  by  the  acidulated  water,  while  the 
fat  and  coloring  matter  remain  in  the  alcoholic  liquid. 

This  fluid  is  now  removed  by  means  of  a  caoutchouc  pipette,  and 
the  hot  acid  solution  repeatedly  extracted  with  fresh  portions  of  the 
alcohol,  until  the  fotty  and  coloring  matters  are  completely  removed ; 
after  which  the  clear  aqueous  liquid  is  concentrated  somewhat  by 
evaporation,  then  supersaturated  with  ammonia,  and  the  mixture  well 
shaken  with  fresh,  hot  amyl  alcohol. 

When  the  liquids  have  separated,  the  amyl  alcohol,  which  now 
contains  the  free  alkaloid,  is  removed  by  means  of  a  pipette,  and  the 
acid  solution  again  extracted  with  a  fresh  portion  of  the  hot  alcohol. 
The  mixed  alcoholic  liquids  are  then  evaporated  to  dryness  on  a 
water-bath,  when  the  alkaloid  will  be  left  often  in  a  sufficiently  pure 
state  for  special  examination.  Should  it,  however,  still  present  a 
yellowish  or  brownish  color,  it  is  again  dissolved  in  very  dilute 
hydrochloric  acid,  the  solution  agitated  with  a  fresh-  portion  of  the 
hot  alcohol,  the  latter  liquid  removed,  and  the  aqueous  solution 
treated  with  excess  of  ammonia,  then  shaken  with  hot  amyl  alco- 
hol, and  this  fluid  separated  and  evaporated  as  before. 

The  authors  of  this  method  cite  a  number  of  experiments  in 
which,  by  it,  they  succeeded  in  recovering  small  quautities  of  mor- 
phine, narcotine,  nicotine,  conine,  and  strychnine,  previously  added 
to  quite  complex  organic  mixtures.  In  one  of  these  experiments, 
about  the  third  of  a  grain  of  morphine  hydrochloride  was  added  to 
a  calfs  stomach,  and  the  latter  exposed  for  a  fortnight  to  the  action 
of  the  sun  and  air;  yet  at  the  end  of  that  time,  although  the  mass 
had  become  thoroughly  putrid,  the  alkaloid  was  recovered,  and  its 
presence  indicated  by  the  reaction  of  ferric  chloride. 

As  morphine  is  quite  soluble  in  amyl  alcohol,  while  it  is  almost 
insoluble  both  in  ether  and  in  chloroform,  the  former  of  these  liquids 
is  very  much  better  adapted  than  either  of  the  latter  for  the  separation 
of  this  alkaloid  from  organic  mixtures.  But  for  the  separation  of 
alkaloids  about  equally  soluble  in  these  three  liquids  we  much  prefer 


426  VEGETABLE   POISONS:    INTRODUCTION. 

the  use  of  ether  or  chloroform  to  that  of  amyl  alcohol,  as  the  latter 
separates  more  slowly  than  either  of  the  others  from  aqueous  mix- 
tures, and  also  requires  a  longer  time  for  its  evaporation.  Moreover, 
as  amyl  alcohol  requires  a  direct  heat  for  its  vaporization,  any  alka- 
loid present  is  much  less  likely  to  be  left  in  its  crystalline  state  than 
when  it  is  deposited  from  ether  or  chloroform  by  spontaneous  evapo- 
ration. Most  of  the  alkaloids  are  more  freely  soluble  in  chloroform 
than  in  amyl  alcohol. 

4.  Process  of  Graham  and  Hofmann. 

This  method  was  first  advised  by  Profs.  Graham  and  Hofmann 
for  the  detection  of  strychnine,  when  present,  in  beer;  but  it  has 
since  been  extended  by  other  experimenters  to  the  separation  of  this 
and  other  alkaloids  from  other  organic  liquids.  It  takes  advan- 
tage of  the  fact  that  when  a  solution  of  strychnine  is  agitated  with 
Charcoal  the  latter  absorbs  the  poison,  and  yields  it  up  to  alcohol 
when  boiled  with  this  liquid.  The  following  are  the  details  of  the 
process,  as  first  employed  by  its  authors. 

Two  ounces  of  ivory-black,  or  animal  charcoal,  were  shaken  in 
half  a  gallon  of  beer  to  which  half  a  grain  of  strychnine  had  been 
purposely  added.  After  standing  for  about  twelve  hours,  the  liquid 
was  found  to  be  nearly  deprived  of  all  bitterness,  the  strychnine 
being  absorbed  by  the  charcoal.  The  liquid  was  now  passed  through 
a  paper  filter,  upon  which  the  charcoal  containing  the  strychnine  was 
collected  and  drained.  The  charcoal  was  then  boiled  for  half  an 
hour  in  eight  ounces  of  ordinary  spirits  of  wine,  avoiding  loss  of 
alcohol  by  evaporation. 

The  alcoholic  liquid  thus  obtained,  which  now  contained  the 
strychnine,  was  next  filtered  and  afterward  submitted  to  distillation. 
A  residual  watery  fluid  was  thus  obtained,  holding  the  strychnine  in 
solution,  but  not  sufficiently  pure  for  the  application  of  tests.  This 
solution  was  rendered  alkaline  by  a  few  drops  of  a  solution  of  potas- 
sium hydrate,  and  then  agitated  with  an  ounce  of  pure  ether.  The 
ethereal  liquid,  when  separated  and  allowed  to  evaporate  spontane- 
ously in  a  watch-glass,  left  the  alkaloid  in  a  state  sufficiently  pure 
for  testing.     [Quart.  Jour.  Chem.  8oc.,  1853,  173.) 

Upon  repeating  this  method,  we  find  that  from  complex  organic 
mixtures  containing  a  very  notable  quantity  of  strychnine  the  alka- 


RECOVERY    BY    DIALYSIS. 


427 


loid  is  extracted  by  the  cliarcoal  in  a  very  nearly  pure  condition,  or 
at  most  requires  only  one  agitation  with  ether  or  ciiloroforni  to  com- 
plete its  puriticiition  ;  but  when  only  a  very  minute  quantity  of  the 
poison  is  present,  it  either  entirely  escapes  detection  or  is  so  contami- 
nated with  foreign  matter  as  to  require  as  many  extractions  with  ether 
or  chloroform,  for  its  purification,  as  to  separate  it  by  either  of  these 
liquids  directly  from  the  prepared  original  mixture.  In  all  cases, 
according  to  our  experience,  this  method  is  attended  with  greater  loss 
of  material  than  to  prepare  the  mixture  according  to  the  process  of 
Stas  and  then  extract  bv  chloroform. 


5.  Method  by  Dialysis. 

Prof.  T.  Graham  has  shown  that  moist  organic  membranes  pos- 
sess the  remarkable  property  of  separating,  when  in  solution,  crys- 
tallizable  substances  from  such  as  are  uncrystallizable,  the  former 
readily  passing  through  such  membranes  when  surrounded  by  a 
liquid,  whereas  the  latter  entirely  fail  thus  to  pass,  or  do  so  only  very 
slowly.  {Jour.  Chem.  Soc,  1862,  216.)  The  first  of  these  classes, 
comprehending  the  crystallizable  substances,  he  named  a^ystalloids, 
the  second  colloids ;  and  to  this  method  of  separation  he  applied  the 
term  dialysis.  The  most  suitable  substance  for  the  dialytic  septum 
is  the  material  known  as  parchment-paper,  which  is  prepared  by 
immersing  unsized  paper  for  a  few  moments  in  a  cold  mixture  of  two 
measures  of  sulphuric  acid  and  one  of  water. 

For  the  application  of  this  method,  a  light  hoop  of  wood,  or, 
better,  of  sheet  gutta-percha,  about  two 
inches  in  depth  and  from  five  to  ten 
inches  in  diameter,  is  covered  with  a 
piece  of  moistened  parchment-paper,  so 
as  to  form  a  sieve-like  vessel  (Fig.  12,  a). 
The  disk  of  paper  used  should  exceed  in 
diameter  the  hoop  to  be  covered  by  three 
or  four  inches,  so  as  to  rise  well  up  the 
outside  of  the  hoop,  and  it  should  be 
bound  to  the  hoop  by  a  string  or  by  an 
elastic  band,  but  it  should  not  be  firmly 

secured.  The  parchment-paper  must  be  entirely  free  from  rents  or 
pores.  Its  soundness  may  be  ascertained  by  sponging  the  upper  sur- 
face with  pure  water  and  then  observing  whether  wet  spots  appear  on 


Fig.  12. 


Graham's  apparatus  for  tfae  applica- 
tion of  dialysis. 


428  VEGETABLE  POISONS  :    INTRODUCTION. 

the  opposite  side :  in  case  they  do,  the  defects  may  be  remedied  by 
applying  liquid  albumen,  and  then  coagulating  this  by  heat.  The 
vessel  thus  prepared  is  called  the  dialyser. 

The  liquid  mixture  to  be  examined  is  now  poured  into  the 
dialyser,  upon  the  surface  of  the  parchment-paper,  but  only  in  such 
quantity  as  at  most  not  to  exceed  about  half  an  inch  in  depth.  The 
vessel,  with  its  contents,  is  then  floated  in  a  basin  (6,  Fig.  12)  con- 
taining a  quantity  of  pure  water  about  four  or  five  times  greater 
than  the  volume  of  liquid  in  the  dialyser.  Any  crystalloidal  matter 
present,  whether  mineral  or  organic,  will  now  begin  to  pass  through 
the  parchment-paper  into  the  water  in  the  larger  vessel,  and  in 
twenty-four  hours  about  two-thirds  or  more  of  it  may  be  found  in 
the  outer  liquid,  or  diffusate,  as  the  latter  is  called.  In  most  in- 
stances the  diffusion  is  much  promoted  by  the  application  of  a  gentle 
heat. 

The  diffusate  is  then  concentrated,  on  a  water-bath,  to  a  small 
volume  or  evaporated  to  dryness,  and  the  residue,  if  sufficiently  pure, 
examined  by  appropriate  reagents.  If,  however,  the  residue  is  unfit 
for  special  testing,  as  will  usually  be  the  case,  at  least  in  the  case  of 
the  alkaloids,  it  is  further  purified  by  extraction  with  ether  or  chloro- 
form, and  then  examined. 

In  a  number  of  experiments  by  this  method,  for  the  separation 
of  small  quantities  of  different  alkaloids  from  complex  organic 
liquids,  we  were  much  disappointed  in  the  results,  they  always 
falling  far  short  of  what  we  anticipated,  especially  in  regard  to  the 
purity  of  the  diffused  alkaloid. 

Even  when  the  diffusate  contains  a  quite  notable  quantity  of  the 
poison,  the  amount  of  colloidal  or  amorphous  matter  also  present  in 
the  liquid  is  not  unfrequently  such  as  to  require  for  its  removal  as 
many  operations  and  as  much  labor  as  to  extract  the  alkaloid  at 
once  from  the  original  mixture  by  chloroform  or  ether,  according  to 
the  methods  previously  considered.  Moreover,  when  only  a  minute 
quantity  of  the  vegetable  base  is  present  in  the  mixture  submitted 
to  examination,  as  a  portion  of  the  poison  always  remains  in  the 
dialyser,  it  may  entirely  escape  detection,  even  when  the  quantity 
present  in  the  original  mixture  is  sufficient  to  give  satisfactory 
results  by  the  chloroform  or  ether  method. 

These  results  closely  accord  with  those  obtained  in  similar  exper- 


dragendorff's  mi/iiiod.  429 

iiucnts  by  Dr.  llaivcy  and  others.  Some  <iuantitative  experiments 
in  regard  to  the  merits  of  this  method  for  the  extraction  of  small 
quantities  of  strychnine  will  he  mentioned  hereafter,  in  the  special 
consideration  of  that  alkaloid. 

From  the  fact  that  in  poisoning  by  metallic  compounds  the  quan- 
tity present  is  ticnerally  much  greater  than  in  poisoning  by  vegetable 
substances,  and,  also,  as  the  former  usually  diffuse  somewhat  more 
readily  than  the  latter  through  membranes,  dialysis  seems  better 
adapted,  in  medico-legal  examinations,  for  the  detection  of  mineral 
than  of  organic  poisons. 

6.  Dragendorff's  Method. 

For  the  recovery  of  the  alkaloids  and  allied  principles  from  organic 
mixtures.  Prof.  Dragendorff  has  advised  (Gericht.  Chem.  JErmittel. 
Giften,  1876,  141)  to  extract  the  finely  divided  substance  with  water 
acidulated  with  sulphuric  acid  at  40°-50°  C.  (104°-122°  F.)  for  a 
few  hours;  this  operation  is  repeated  two  or  three  times,  and  the 
strained  and  filtered  liquids  united.  The  mixed  liquids  are  concen- 
trated to  a  syrupy  consistence,  and  the  syrup  mixed  with  three  or 
four  times  its  volume  of  alcohol  and  digested  for  twenty-four  hours 
at  about  30°  C.  (86°  F.).  The  cooled  liquid  is  filtered'and  the  solids 
washed  with  70  per  cent,  alcohol.  The  alcoholic  liquid  is  distilled 
in  a  flask  until  the  alcohol  has  been  expelled,  after  which  the  cooled 
aqueous  residue,  diluted  if  necessary,  is  filtered. 

For  the  examination  of  the  extract  thus  prepared  Prof.  Dragen- 
dorff advises  a  very  comprehensive  method,  by  which  not  only  the 
alkaloids  but  also  various  other  vegetable  principles  would  be  re- 
covered, the  steps  of  the  process  being  as  follows : 

I.  The  filtered  liquid,  while  still  acid,  is  violently  agitated  in  a 
flask  at  the  ordinary  temperature  with  freshly  rectified  Petroleum 
Ether,  which  after  the  liquids  have  separated  is  decanted,  and  the 
operation  repeated  as  long  as  the  ethereal  liquid  takes  up  any  matter. 
In  this  manner  much  of  the  coloring  matter,  and  also,  if  present, 
Piperine,  Picric  acid,  Camphor,  and  analogous  bodies,  constituents 
of  Black  hellebore  and  of  Aconite,  Carbolic  acid,  and  certain  essential 
oils,  will  be  removed.  Portions  of  the  petroleum  fluid  may  now  be 
examined  for  these  various  substances. 

II.  The  acid  liquid  is  next  agitated  with  Bexzexe,  which  in  its 
turn  is  removed,  and  the  operation  repeated  with  a  fresh  volume 


430  VEGETABLE  POISO^^S  :  TXTRODUCTION. 

of  benzene  as  long  as  a  portion  of  the  decanted  liquid  leaves  a  residue 
upon  evaporation. 

The  benzene  residue  may  contain  any  of  the  following  substances  : 
Caffeine,  Cantharidin,  Santonin,  Carophyllin,  Cubebin,  Piperine,  Pic- 
ric Acid,  Aloetin,  Digitalin,  Cascarillin,  or  Perberijie,  any  of  which 
may  be  left  more  or  less  crystalline.  And  also,  as  amorphous,  Ela- 
terin,  Popidin,  CoJocynthin,  constituents  of  the  Pimento,  Colchicine, 
Grysammic  Acid,  or  constituents  of  Worinicood  and  of  certain  other 
substances. 

III.  The  acid  aqueous  solution  is  now  extracted  by  Chloro- 
FOEM  in  a  similar  manner.  This  liquid  will  extract,  if  present, 
Cinehonine,  Theobromine,  Papaverine,  Narceine,  Picrotoxin,  Helle- 
horin,  Digitalin,  Convallamarin,  Saponin,  Senegin,  Sniilacin,  Syringin, 
or  Jervine  and  other  constituents  of  the  Hellebores. 

IV.  The  aqueous  liquid  is  again  agitated  with  Petroleum 
Ether,  for  the  purpose  of  remo\'ing  the  last  traces  of  Benzene  and 
Chloroform.  After  removal  of  the  petroleum  ether,  the  acid  aqueous 
liquid  is  rendered  alkaline  by  Aqua.  Ammonise. 

V.  The  ammoniacal  liquid  is  extracted  with  Petroleum  Ether, 
and  the  fluid  decanted.  The  Petroleum  residue  may  contain  either 
Strychnine,  Quinine,  Sabadilline,  Brucine,  Veratrine,  Emetin,  Co- 
nine, Methyl  Conine,  Nicotine,  Alkaloid  of  Capsicum,  Sarracinin, 
Lobeline,  Sparteine,  Trimethylamine,  Aniline,  or  the  volatile  alkaloid 
of  Pimento. 

VI.  The  aqueous  ammoniacal  liquid  is  now  treated  in  like  man- 
ner with  Bexzexe.  This  liquid  will  extract,  if  present,  Atrojnne, 
Syoscyamine,  Strychnine,  Ethyl-  and  Methyl-Strychnine,  Quinine  and 
Quinidine,  Cinehonine,  Narcotine,  Codeine,  Acolyctin,  Sabadilline, 
Thebaine,  Brucine,  Physostigmine,  Veratrine,  Sebatrin,  Delphinine, 
Nepalin,  Aconitine,  Napellin,  Emetin,  and  the  alkaloid  of  Aconitum 
Lycoctonum. 

VII.  The  ammoniacal  solution  is  next  agitated  with  Chloro- 
form, which  mav  extract  Morphine,  Cinehonine,  Papaverine,  Nar- 
ceine, and  the  alkaloid  of  Celandine. 

VIII.  The  alkaline  liquid  is  now  agitated  with  Amyl  Alco- 
hol, which  will  take  up  any  Morphine,  Solanine,  or  Salicin  present ; 
and,  also,  any  Narceine,  Saponin,  Senegin,  and  Convallamarin  that 
mav  not  have  been  withdrawn  in  the  previous  extractions. 

IX.  Finally,  the   ammoniacal   fluid    is    mixed  with    powdered 


PTOMAINES.  431 

glass  and  evaporated  to  dryness,  and  (lio  pulverized  residue  extracted 
bv  Chloroform,  wliidi  will  dissolve  any  Oirarine  present. 

Although  the  foregoing  method  of  Dragendorff  provides  for  tiie 
recovery  of  a  great  number  and  variety  of  organic  substances,  yet  as 
very  few,  if  any,  of  these  bodies  are  wholly  insoluble  in  the  different 
extra(!ting  liquids  employed,  the  substance,  unless  present  in  very 
notable  quantity,  might  be  entirely  removed  from  the  aqueous  solu- 
tion before  the  conditions  best  adapted  for  its  recovery  were  reached. 

For  example,  moi'phine  and  its  sulphate  are  not  absolutely 
insoluble  in  any  of  the  liquids  named,  yet  before  employing  the 
liquid  in  which  this  alkaloid  is  rather  freely  soluble,  namely,  amyl 
alcohol,  the  solution  would  have  been  extracted  some  .seven  different 
times  with  various  liquids,  and  these  employed  to  about  exhaustion. 

In  regard  to  morphine,  there  is  no  doubt  that  if  sufficient  of  the 
alkaloid  is  present  to  carry  it  through  these  various  washings,  that 
portion  finally  recovered  by  the  amyl  alcohol  w^ould  be  somewhat  or 
even  very  much  purer  than  if  extracted  at  once  from  the  prepared 
aqueous  solution  by  rendering  the  latter  alkaline  and  agitating  it 
with  the  alcohol.  But  as  to  this  quantity  being  present,  especially 
of  the  absorbed  poison,  even  under  apparently  the  most  favorable  con- 
ditions, there  is  no  certainty.  Hence  in  medico-legal  investigations 
we  w'ould  hesitate  to  employ  this  method,  at  least  in  all  its  details; 
unless,  perchance,  there  was  no  clue  whatever,  either  from  symptoms 
or  other  circumstances,  as  to  at  least  the  general  nature  of  the  poison 
taken.  It  very  rarely  happens  that  some  knowledge  of  this  kind  is 
not  at  hand. 

Recently  Profs.  Guareschi  and  Mosso  [Arch.  Ital.  Biol,  1883) 
have  strongly  objected  to  the  method  of  Dragendorff,  on  the  ground 
that  on  evaporation  of  the  organic  mixture  the  free  sulphuric  acid 
present  may  give  rise  to  alkaloidal  substances  (ptomaines),  due  to  the 
decomposing  action  of  the  acid.  And  this  objection  has  been  sus- 
tained by  F.  Coppola  [Gazzetta  Chim.  Ital.,  xii.  11,  511)  in  experi- 
ments on  fresh  dog's  blood,  examined  after  this  method. 

Ptomaines. — This  name  was  applied  by  Prof.  Selmi  to  certain 
basic  bodies  or  principles  developed  during  the  putrefactive  decompo- 
sition of  animal  substances.  Like  principles  have  since  been  found 
in  certain  pathological  conditions,  and  even,  according  to  some  ob- 


432  VEGETABLE   POISONS:   INTEODUCTION. 

servers,  in  normal  tissues  and  secretions.  The  exact  conditions  under 
which  these  substances  develop  have  not  as  yet  been  fully  deter- 
mined. The  toxic  symptoms  produced  by  spoiled  food  may  in  some 
instances,  perhaps,  be  due  to  the  presence  of  these  bodies. 

Some  of  the  ptomaines  are  said  to  be  inert;  others  are  more  or 
less  poisonous,  producing  in  some  instances  symptoms  similar  to  those 
occasioned  by  certain  vegetable  alkaloids.  Some  are  described  as 
liquid  and  volatile,  others  as  fixed  and  crystallizable.  For  the  most 
part  they  are  more  or  less  freely  soluble  in  ether,  in  chloroform,  and 
in  benzene;  but  some  are  insoluble  in  one  or  more  of  these  liquids. 
The  ptomaine  salts  are  generally  freely  soluble  in  water. 

The  ptomaines  have  usually  an  alkaline  reaction,  and  yield  pre- 
cipitates with  phosphomolybdic  acid,  iodized  potassium  iodide,  pla- 
tinic  and  auric  chlorides,  and  with  certain  other  general  reagents  for 
the  alkaloids.  In  no  instance  has  a  substance  of  this  kind  been 
found  that  fully  responds  to  the  special  reactions  of  any  known  vege^ 
table  alkaloid. 

A  very  elaborate  and  important  contribution  to  this  subject  has  re- 
cently been  made  by  Profs.  Guareschi  and  Mosso  (J.rc/i.  Ital.  Biol., 
1883).  In  some  preliminary  experiments  these  observers  found  that 
commercial  alcohol  on  evaporation  with  an  acid  very  frequently 
leaves  a  residue  having  alkaloidal  reactions ;  that  a  similar  residue 
may  be  obtained  from  ordinary  chloroform  and  ether;  and  that 
the  purest  commercial  amyl  alcohol  and  benzene  contain  pyridine. 
Hence  these  authors  conclude  that  the  results  obtained  by  previous 
observers,  in  which  these  liquids,  especially  amyl  alcohol  and  ben- 
zene, were  employed  for  the  extractions,  have  no  value  whatever. 

From  thirty-six  kilogrammes  (ninety-six  pounds  troy)  of  human 
brains,  which  had  been  allowed  to  putrefy  at  the  ordinary  tempera- 
ture for  about  two  months,  Guareschi  and  Mosso  obtained  only  a  very 
minute  quantity  of  ptomaines,  the  amount  being  too  small,  especially 
in  view  of  the  physiological  experiments  they  desired  to  make,  to 
determine  its  composition.  Administered  hypodermically  to  frogs  in 
doses  ranging  from  0.0125  to  0.3  gramme  (l-5th  to  5  grains),  this 
extract  produced  symptoms  similar  to  those  occasioned  by  curare; 
but  it  was  much  less  energetic  in  its  action,  the  latter  quantity  being 
required  to  prove  fatal.  According  to  these  observers,  the  extract 
obtained  from  human  brains  could  not  be  confounded  in  its  proper- 
ties with  any  known  poison. 


PTOMAINES. 


433 


From  eighty  kilogrammes  (two  Imndrecl  and  thirteen  pounds)  of 
fibrin  from  putrid  ox-blood  five  months  old  an  extract  was  obtained 
which  had  alkaloidal  reactions,  and  a  physiological  action  similar  to 
the  extract  from  human  brains.  On  extracting  fresh  beef  according 
to  the  method  of  DragendorflP,  Profs.  Guareschi  and  Mosso  obtained 
a  final  residue  which  readily  gave  evidence  of  the  presence  of  alka- 
loiilal  substances  ;  whilst  when  tartaric  acid  was  employed  as  the 
acidifying  agent  instead  of  sulphuric  acid,  a  much  smaller  extract 
was  obtained,  and  this  had  the  properties  of  the  extract  from  putrid 
fibrin.  These  results  led  these  observers,  as  already  stated,  to  c(m- 
demn  strongly  the  method  of  Dragendorff  for  medico-legal  inves- 
tigations. 

Still  more  recently,  F.  Marino-Zuco  {Gazzetta  Chim.  Ital.,  xiii. 
431)  obtained  from  white  and  yolk  of  egg,  brains,  lungs,  heart,  liver, 
spleen,  and  blood,  most  carefully  examined  after  several  methods, 
all  the  conditions  of  the  respective  authors  being  observed,  a  basic 
substance  having  alkaloidal  reactions  and  identical  in  composition 
with  neurine.  This  neurine  was  found  to  originate,  not,  as  is  gener- 
ally supposed,  from  alterations  of  the  proteids,  but  from  the  splitting 
up  of  the  lecithins  under  the  influence  of  acids  or  alkalies.  On 
applying  the  same  method  to  the  albumen  remaining  after  complete 
extraction  of  the  lecithins  from  egg,  brain,  lungs,  and  like  substances, 
the  result  was  purely  negative. 

Since  neurine  hydrochloride  is  not  decomposed  by  acid  sodium 
oarbonate  (bicarbonate),  this  author  was  able  to  separate  completely 
the  hydrochlorides  of  a  vegetable  alkaloid  and  of  the  so-called 
ptomaines  by  rendering  the  aqueous  solution  of  the  mixed  salts  alka- 
line by  the  sodium  salt,  and  agitating  the  mixture  with  the  proper 
solvent  for  the  alkaloid.  The  alkaloid  alone  is  thus  extracted,  the 
neurine  remaining  in  the  aqueous  fluid  as  hydrochloride.  [Jour. 
Chem.  Soc.  AbsL,  March,  1884,  342.) 

From  the  foregoing  statements  it  is  obvious  that  much  uncertainty 
still  exists  in  regard  to  the  nature  and  production  of  the  so-called 
ptomaines;  yet,  admitting  their  existence,  there  seems  to  be  little 
danger  of  the  experienced  observer  confounding  these  substances 
with  the  vegetable  alkaloids,  especially  when  the  ordinary  methods 
and  pure  reagents  are  employed  for  the  extraction. 


28 


434  NICOTLNE. 


CHAPTEE   I 

VOLATILE  ALKALOIDS:    iSTICOTINE,  CONINE 

Section  I. — Nicotine.     (Tobacco.) 

History. — Nicotine,  nieotina,  or  nicotia,  is  the  active  principle  of 
the  common  tobacco  plant,  Nieotiana  Tabacum,  in  which  it  occurs  in 
combination  with  malic  acid ;  it  exists  in  the  leaves,  root,  and  seeds 
of  the  plant,  and  also  in  the  smoke  of  tobacco.  Nicotine  is  destitute 
of  oxygen,  its  formula  being  CioHi4]Sr2.  Vauquelin,  in  1809,  was 
the  first  to  attempt  the  separation  of  this  active  principle,  and  he 
succeeded  in  discovering  some  of  the  properties  of  some  of  its  com- 
pounds, but  failed  to  isolate  the  pure  alkaloid.  Posselt  and  Rei- 
mann,  in  1828,  were  the  first  to  separate  the  alkaloid;  in  1842, 
Ortigosa  analyzed  some  of  its  compounds,  and  Barral  analyzed  nico- 
tine itself.     [Gmelin's  Hand-book,  xiv.  220.) 

Preparation. — jSTicotine  may  be  prepared,  as  first  proposed  by 
M.  Schloesing,  in  the  following  manner.  Coarsely  powdered  tobacco 
is  boiled  with  water,  the  cooled  liquid  strained  through  linen,  then 
evaporated  to  the  consistency  of  a  syrup,  and  while  hot  agitated  with 
twice  its  volume  of  alcohol  of  sp.  gr.  0.837.  After  standing  some 
time,  the  liquid  portion  of  the  mixture,  which  contains  the  whole  of 
the  vegetable  base,  is  decanted  from  the  black  and  almost  solid  de- 
posit, then  concentrated,  and  mixed,  while  still  warm,  with  a  solution 
of  potassium  hydrate,  by  which  the  alkaloid  will  be  set  free.  The 
cooled  mixture  is  agitated  with  ether,  which  will  dissolve  the  liber- 
ated base,  together  with  some  coloring  matter.  After  repose,  the 
ethereal  liquid  is  decanted  and  agitated  with  powdered  oxalic  acid, 
when,  after  a  time,  the  oxalate  of  nicotine  thus  formed  will  subside 
as  a  syrupy  mass.  This,  after  the  decantation  of  the  ether,  is  washed 
with  fresh  ether,  then  rendered  alkaline  with  potassium  hydrate,  and 


PHYSIOLOGICAL    EFFECTS.  435 

again  agitated  with  ether,  which  will  now  dissolve  the  alkaloid.  The 
ethereal  solution  is  transferred  to  a  retort,  the  ether  distilled  off,  and 
the  residue  exposed  for  some  hours,  at  a  temperature  of  about  140°  C. 
(284°  F.),  to  a  current  of  hydrogen  gas,  by  which  the  last  traces  of 
ether,  water,  and  ammonia  will  be  separated;  the  heat  is  then  in- 
creased to  about  180°  C.  (356°  F.),  when  the  alkaloid  will  distil 
over  pure  and  colorless. 

According  to  Dr.  J.  Skalweit,  the  process  of  Schloesing  yields 
unreliable  results  for  the  quantitative  determination  of  the  nicotine 
present  in  tobacco,  and  he  advises  to  convert  the  alkaloid  into  sul- 
phate, and  then  extract  this  salt  with  98  per  cent,  alcohol.  {Amer. 
Jour.  Fharm.,  Feb.  1882,  60.) 

The  proportion  of  nicotine  varies  greatly  in  different  kinds  of 
tobacco.  According  to  Schloesing  {Chem.  Gaz.,  v.  43),  some  dried 
French  samples  contain  from  7  to  8  per  cent,  of  the  alkaloid ;  Vir- 
ginia and  Kentucky,  6  or  7  per  cent. ;  while  Maryland  and  Havana 
contain  only  about  2  per  cent.,  which  is  about  the  proportion  found 
in  ordinary  snuff. 

According  to  some  observers,  the  smoke  of  tobacco  does  not  con- 
tain nicotine;  but  Melsens  has  fully  established  the  existence  of  the 
alkaloid  in  tobacco-smoke,  and  he  places  the  quantity  at  about  0.7 
per  cent,  of  the  weight  of  the  tobacco  consumed,  and  about  15  per 
cent,  of  the  total  quantity  of  nicotine  contained  in  tobacco.  (Jour. 
Chem.  Soc.  AbsL,  Aug.  1882,  906.) 

Nicotine  is  a  transparent,  colorless,  oily  liquid,  and  one  of  the 
most  active  poisons  known,  even  equalling  in  the  rapidity  of  its 
action  hydrocyanic  acid.  There  are,  however,  perhaps,  only  two  in- 
stances yet  recorded  of  poisoning  of  the  human  subject  by  this  sub- 
stance in  its  pure  form ;  but  poisoning  by  tobacco,  which  owes  its 
activity  entirely  to  this  alkaloid,  is  not  of  unfrequent  occurrence. 
The  following  consideration  in  regard  to  the  physiological  effects 
of  the  alkaloid  will,  therefore,  be  based  chiefly  upon  its  action  as 
observed  in  cases  of  poisoning  by  tobacco. 

Symptoms. — The  usual  effects  produced  by  a  poisonous  dose  of 
tobacco,  when  taken  into  the  stomach,  are  confusion  in  the  head, 
paleness  of  the  countenance,  vertigo,  nausea,  severe  retching  and 
vomiting,  heat  in  the  stomach,  great  anxiety,  a  sense  of  sinking  at 
the  pit  of  the  stomach,  with  extreme  prostration,  trembling  of  the 
limbs,  and  sometimes  violent  purging.    The  pulse  is  small,  feeble,  and 


436  nicotijSte. 

almost  imperceptible ;  the  respiration  difficult,  and  the  skin  cold  and 
clammy ;  the  pupils  are  generally  dilated,  but  sometimes  contracted, 
and  the  vision  is  usually  more  or  less  impaired.  Death  is  often 
preceded  by  convulsions  and  paralysis. 

In  regard  to  the  operation  of  tobacco,  Dr.  Pereira  remarks  that 
it  resembles  that  of  Lobelia  inflata.  With  foxglove,  tobacco  agrees 
in  several  particulars,  especially  in  that  of  enfeebling  the  action  of 
the  vascular  system,  though  its  power  in  this  respect  is  inferior  to 
that  of  foxglove.  In  its  capability  of  causing  relaxation  and  depres- 
sion of  the  muscular  system  and  trembling,  tobacco  surpasses  fox- 
glove; as  it  does,  also,  in  its  power  of  promoting  the  secretions. 
From  belladonna,  stramonium,  and  hyoscyamus  it  is  distinguished 
by  causing  contraction  of  the  pupil,  both  when  applied  to  the  eye 
and  when  taken  internally  in  poisonous  doses,  and  also  by  the  absence 
of  delirium  and  of  any  affection  of  the  parts  about  the  throat.  [Mat 
Med.,  ii.  494.) 

A  singular  case  is  related  {Jour,  de  Chim.  MM.,  1869,  565)  in 
which  a  man  accustomed  to  smoking  took  into  his  mouth  for  the 
first  time  a  bolus  of  tobacco,  and  after  a  quarter  of  an  hour  involun- 
tarily swallowed  the  mass.  An  hour  later  he  became  unconscious, 
and,  although  the  usual  remedies  were  employed,  he  became  worse 
and  expired,  without  at  any  time  having  recovered  consciousness. 

Administered  in  the  form  of  clyster^,  tobacco  has  in  several  in- 
stances caused  death.  In  a  case  of  this  kind  quoted  by  Dr.  Chris- 
tison,  in  which  an  enema  prepared  by  boiling  about  an  ounce  of 
tobacco  for  fifteen  minutes  in  water  was  administered  by  the  advice 
of  a  quack  to  an  individual  laboring  under  obstinate  constipation, 
the  patient  was  seized  in  two  minutes  afterward  with  vomiting,  vio- 
lent convulsions,  and  stertorous  breathing,  and  died  in  three-quarters 
of  an  hour. 

So,  also,  the  external  application  of  tobacco  to  abraded  surfaces, 
and  even  to  the  healthy  skin,  has  been  attended  with  violent  symp- 
toms, and  even  death.  In  a  case  of  this  kind,  in  which  a  man 
applied  to  himself  a  decoction  of  tobacco  for  the  cure  of  an  eruptive 
disease,  death  took  place  in  three  hours  with  the  usual  symptoms  of 
tobacco  poisoning.     (See  Amer.  Jour.  Med.  Sci.,  Jan.  1865,  268.) 

Even  the  smoking  of  tobacco  has  been  known  to  produce  danger- 
ous and  even  fatal  results.  Dr.  Marshall  Hall  relates  the  case  of 
a  young  man,  who,  having  smoked  two  pipes  of  tobacco,  was  seized 


PERIOD    WHEN    FATAL.  437 

with  iiaiisoa,  v()initin<^,  syiic<ti)t',  stiij)»»r,  stertorous  broatliin}^,  and 
u;('iu'ial  spasms:  after  a  time  lie  recovered.  Gmelin  mentions  two 
onuses  of  (lentil,  caused  in  one  instance  by  the  smoking  of  seventeen, 
and  in  the  other  of  eighteen,  pipes  of  tobacco  at  a  sitting.  In 
another  case,  in  which  a  man  during  a  period  of  leas  than  twelve 
hours  smoked  forty  cigarettes  and  fourteen  full-sized  cigars,  death 
took  jjlace  from  the  effects  on  the  evening  of  the  following  day. 

A  most  remarkable  case  of  poisoning  hy  nicotine  in  its  pure  state 
occurred  in  Belgium,  in  1850,  for  which  the  Count  de  Bocarm6  was 
condemned  to  death,  the  person  murdered  being  his  brother-in-law, 
Gustave  Fougnies.  An  unknown  quantity  of  the  poison  was  forci- 
bly administered,  and  it  is  believed  that  death  took  place  within  five 
minutes  afterward.  Nicotine  was  detected  in  small  quantity  by  M. 
Stas  in  the  mouth,  throat,  stomach,  liver,  and  spleen  of  the  deceased, 
and  also  in  the  floor  near  which  the  act  was  committed.  {Orjila's 
Toxicology,  ii.  498.)  Tiie  only  other  related  case  of  poisoning  by 
this  alkaloid  in  its  pure  state  occurred  in  London,  in  1858,  and 
death  took  place  in  from  three  to  five  minutes  after  the  poison  had 
been  taken.  In  this  case  a  small  quantity  of  the  poison  was  detected 
by  Dr.  Taylor  in  the  contents  of  the  stomach. 

Experiments. — In  this  connection,  we  may  briefly  relate  the  fol- 
lowing experiments  in  regard  to  the  action  of  nicotine  in  its  pure 
state  upon  animals,  (a)  One  drop  of  the  poison  placed  in  the  mouth 
of  a  full-grown  cat  produced  immediate  prostration,  continued  con- 
vulsive movements  of  the  extremities,  and  death  in  seventy-eight 
seconds  after  the  poison  had  been  administered.  (6)  In  another 
case,  a  small  drop  was  ]>laced  on  the  tongue  of  a  cat.  In  ten  seconds 
the  animal  fell  on  the  right  side  perfectly  prostrated,  then  had  con- 
vulsive movements  of  the  legs,  voided  urine,  and  died  in  two  min- 
utes and  a  half,  (c)  A  third  cat,  to  which  a  similar  quantity  had 
been  administered,  fell  in  about  twelve  seconds,  had  violent  convul- 
sions of  the  extremities,  and  was  dead  in  seventy-Jive  seconds  after 
taking  the  poison. 

Period  when  Fated. — In  fatal  poisoning  by  tobacco,  death  does 
not  usually  occur  until  after  some  hours,  but  it  may  take  place 
within  a  very  much  shorter  period.  In  a  case  in  which  about  an 
ounce  of  crude  tobacco  had  been  swallowed,  death  took  place  in 
about  seven  hours ;  while  in  another,  an  unknown  quantity  of  snuff 
administered  in  whiskey  proved  fatal  in  about  one  hour. 


438  NICOTINE. 

Most  of  the  reported  cases  of  death  from  tobacco  have  been 
occasioned  by  its  use  in  the  form  of  clyster.  M.  Tavignot  relates 
a  case  in  which  an  injection  prepared  by  mistake  with  nearly  two 
ounces  of  tobacco  (sixty  grammes),  instead  of  nine  grains  and  a 
quarter  (sixty  centigrammes),  was  administered  to  a  stout  man,  aged 
fifty-five  years.  In  seven  or  eight  minutes  afterward  he  was  seized 
with  stupor,  headache,  paleness  of  the  face,  pain  in  the  abdomen, 
indistinct  articulation,  and  convulsive  tremors,  at  first  of  the  arms, 
then  of  the  whole  body.  These  symptoms  were  soon  followed  by 
extreme  prostration  and  slow  laborious  breathing,  and  then  coma, 
which  terminated  fatally  in  about  eighteen  minutes  after  the  injection 
had  been  administered.  {Gazette  Med.  de  Paris,  Nov.  1840,  763.) 
In  a  case  quoted  by  Dr.  Beck  {Med.  Jur.,  ii.  878),  a  female  affected 
with  worms  used  an  enema  of  tobacco,  and  was  soon  seized  with 
violent  convulsions,  and  died  from  its  effects  fifteen  minutes  after- 
ward. 

Fatal  Quantity. — In  most  of  the  fatal  cases  of  poisoning  from 
the  swallowing  of  tobacco,  the  quantity  taken  could  not  be  accurately 
determined.  In  a  case  reported  by  Mr.  Skae,  a  man  who  had  swal- 
lowed a  large  mouthful  of  crude  tobacco  became  suddenly  insensible, 
motionless,  and  relaxed,  with  contracted  pupils,  and  a  scarcely  per- 
ceptible pulse.  These  symptoms  were  followed  by  convulsions,  loud 
cries,  dilated  pupils,  active  vomiting  and  purging,  and  death  by 
syncope.     {8tille's  Mat.  Med.,  ii.  298.) 

Administered  in  the  form  of  enema,  tobacco  has  proved  fatal 
in  comparatively  small  quantity.  Thus,  several  instances  are  re- 
ported in  which  a  decoction  of  a  drachm  exhibited  in  this  manner 
caused  death.  In  one  of  these,  quoted  by  Dr.  Christison,  death 
took  place  in  thirty-five  minutes.  In  a  case  cited  by  Dr.  Pereira 
{Mat.  Med.,  ii.  494),  an  injection  containing  only  half  a  drachm  was 
followed  by  fatal  results. 

Treatment. — This  consists  in  the  speedy  removal  of  the  poison, 
in  case  it  has  been  swallowed,  from  the  stomach;  and  the  subse- 
quent exhibition  of  stimulants.  Animal  charcoal,  tannic  acid,  and 
an  aqueous  solution  of  iodine  in  potassium  iodide  have  been  advised 
as  chemical  antidotes.  Opium  may  sometimes  be  found  useful  to 
allay  the  excessive  vomiting. 

Post-mortem  Appearances. — These  are  subject  to  great  varia- 
tion.    In  a  case  quoted  by  Dr.  Taylor  {On  Poisons,  747),  in  which 


GENERAL   CHEMICAL    NATURE.  439 

something  less  tlian  an  ounce  of"  crude  tobacco  had  been  swallowed 
and  death  occurred  in  about  seven  hours,  the  following  appearances 
were  observed  forty  Jiours  after  death.  The  sul)stance  of  the  brain 
and  the  upper  part  of  the  sjiiiiai  marrow  were  somewhat  congested  ; 
the  heart  was  empty,  small,  and  contracted  ;  and  the  liver  and  kid- 
neys were  much  congested.  The  mucous  membrane  of  the  stomach 
presented  several  red  patches.  The  intestines  were  contracted  through- 
out, and  contained  only  a  mucous  fluid  tinged  with  blood  ;  the  mucous 
membrane  was  of  a  red  color,  partially  abraded,  and  full.  The 
bladder  was  contracted  and  empty.  The  blood  throughout  the  body 
was  dark-colored  and  liquid. 

In  a  case  in  which  an  enema  prepared  with  about  an  ounce  of 
tobacco  proved  fatal  in  three-quarters  of  an  hour,  the  only  abnormal 
appearances  observed  two  days  after  death  were  a  gorged  condition 
and  redness  of  the  inner  and  outer  coats  of  the  large  and  small  intes- 
tines, and  patches  of  extravasation  in  some  parts  of  the  mucous 
membrane,  together  with  an  empty  state  of  the  heart  and  of  the 
blood-vessels  of  the  abdomen.    The  stomach  and  brain  were  natural. 

CHEMiCAii  Properties. 

General  Chemical  Nature. — Nicotine,  when  perfectly  pure, 
is  a  transparent,  colorless,  oily  liquid,  having  a  strong  alkaline  reac- 
tion, and  a  density  of  about  1.048.  Its  odor  is  usually  described  as 
acrid,  unpleasant,  and  resembling  somewhat  that  of  tobacco  :  this 
is  true  of  most  samples  as  met  with  in  the  shops,  but  when  perfectly 
pure  it  has,  as  remarked  by  Otto,  a  rather  pleasant  ethereal  odor. 
The  odor  may  be  perceived,  but  is  not  characteristic,  in  a  few  drops 
of  a  pure  l-50,000th  aqueous  solution  of  the  alkaloid. 

Nicotine  has  a  pungent,  acrid  taste,  even  when  highly  diluted, 
producing  a  peculiar  sensation  in  the  throat  and  air-passages.  It 
slowly  distils  at  about  146°  C.  (295°  F.),  and  boils  at  about  243.5°  C. 
(470°  F.),  recondensing  for  the  most  part  unchanged  ;  in  an  atmos- 
phere of  hydrogen  gas  it  may  be  distilled  without  any  decomposition. 
It  imparts  a  transient  greasy  stain  to  white  paper,  and  burns  with 
a  white,  smoky  flarae.  On  exposure  to  the  air,  nicotine  slowly  be- 
comes yellow,  then  brownish  and  thick,  being  finally  converted  into 
a  resinous  mass. 

Solubility. — Nicotine  is  freely  soluble  in  all  proportions  in  water ; 
it  is  also  soluble  in  alcohol,  ether,  chloroform,  the  fixed  oils,  and  in 


440  NICOTINE. 

oil  of  turpentine.  By  the  use  of  some  of  these  latter  solvents  the 
alkaloid  may  be  extracted  to  a  greater  or  less  extent  from  its  solu- 
tion in  water.  For  this  purpose  ether  has  usually  been  employed^ 
but  this  liquid  is  inferior  in  this  respect  to  chloroform,  as  may  be 
seen  from  the  following  experiments. 

1.  Extraction  by  Ether. — When  one  volume  of  a  1-lOOth  aqueous 
solution  of  nicotine  is  agitated  with  jive  volumes  of  absolute  ether ^ 
and  the  latter  liquid,  after  repose,  decanted,  the  aqueous  solution 
yields  with  reagents  somewhat  better  reactions  of  the  presence  of 
nicotine  than  a  pure  l-500th  solution  of  the  alkaloid ;  thus  showing 
that  the  ether  extracted  less  than  four-fifths  of  the  vegetable  base. 
When  a  1-lOOth  solution  is  agitated  with  twenty-five  volumes  of 
ether,  the  aqueous  liquid  is  reduced  to  about  a  l-1200th  solution. 
Experiments  made  with  aqueous  solutions  of  the  hydrochloride  of 
nicotine,  by  decomposing  the  salt  with  potassium  hydrate  and  then 
extracting  with  absolute  ether,  gave  results  similar  to  those  just 
mentioned ;  as  did  also  experiments  in  which  concentrated  com- 
mercial ether  was  employed  as  the  extracting  liquid. 

'  2.  By  Chloroform. — When  a  1-1 00th  aqueous  solution  of  pure 
nicotine  is  agitated  with  five  volumes  of  pure  chloroform,  and  the 
latter  carefully  decanted,  the  former  liquid  is  reduced  to  about  a 
l-4000th  solution  of  the  alkaloid.  So,  also,  under  like  circum- 
stances, a  1-lOOOth  aqueous  solution  is  reduced  to  about  a  l-40,000th 
solution.  These  experiments  show  that  under  these  conditions  chlo- 
roform separates  about  39-40ths  of  the  alkaloid. 

Special  Chemical  Properties. — If  a  drop  of  nicotine  be 
placed  in  a  watch-glass,  and  this  covered  by  a  similar,  inverted  glass 
containing  a  small  drop  of  either  hydrochloric  or  nitric  acid,  the 
glasses  become  filled  with  white  fumes.  These  fumes  are  not  so 
dense  as  those  obtained  from  conine  under  similar  circumstances ;  nor 
are  they,  as  in  the  case  of  conine,  attended  with  the  formation  of 
crystals.  When  the  pure  alkaloid  is  treated  directly  with  concen- 
trated hydrochloric  acid,  it  yields  a  syrupy  liquid,  without  the  forma- 
tion of  crystals;  with  nitric  acid  it  yields  a  reddish  syrupy  fluid. 
When  the  alkaloid  is  touched  with  concentrated  sulphuric  acid,  it 
undergoes  little  or  no  change  until  the  mixture  is  heated,  when 
it  acquires  a  brownish  color.  It  need  hardly  be  added  that  these 
reactions  in  themselves  are  not  characteristic  of  this  alkaloid. 

A  pure  aqueous  solution  of  nicotine  is  colorless,  has  the  peculiar 


PI.ATINIC    CHLOIUDK    TKST.  Ill 

odor  and  taste  t)t' tlic  alkaloid,  and  an  alkaline  reaction,  Wli(;n  snch 
a  solution  is  distilled,  the  alkaloid  passes  over  with  the  vapor  of 
water.  Nicotine  readily  unites  with  acids,  forming  salts,  some  of 
which  are  readily  crystallizable. 

The  salts  of  nicotine  have  the  peculiar  taste  of -the  alkaloid,  hut 
are  destitute  of  odor.  They  arc  mostly  soluble  in  water  and  in  alco- 
hol, but  insoluble  in  ether.  Their  aqueous  solutions  lose  part  of  the 
alkaloid  upon  evaporation,  and  are  decomposed  by  the  mineral  alka- 
lies, evolving  the  odor  of  nicotine.  When  such  an  alkaline  mixture 
is  agitated  with  chloroform,  this  liquid,  after  decantation  and  evapo- 
ration, leaves  the  extracted  alkaloid  in  the  form  of  oily  drops  or 
streaks.  On  distilling  a  solution  of  a  salt  of  nicotine  which  has  been 
treated  with  excess  of  potassium  or  sodium  hydrate,  the  free  alkaloid 
will  be  found  in  the  distillate,  together  with  any  ammonia  that  may 
have  been  present  in  the  mixture.  If  the  distillate  thus  obtained 
be  neutralized  with  oxalic  acid,  then  gently  evaporated  to  dryness, 
and  the  residue  treated  with  alcohol,  this  liquid  will  dissolve  the 
oxalate  of  nicotine  produced  by  the  neutralization,  while  any  ammo- 
nium oxalate  present  will  remain,  it  being  insoluble  in  this  men- 
struum. On  now  evaporating  the  alcoholic  solution  to  dryness,  the 
oxalate  of  nicotine  may  be  obtained  in  its  pure  state. 

In  the  following  examinations  of  the  limit  of  different  tests  for 
nicotine  when  in  solution,  the  pure,  colorless  alkaloid  was  dissolved 
in  distilled  water.  The  fractions  indicate  the  fractional  part  of  a 
grain  of  the  alkaloid  in  solution  in  one  grain  of  water.  The  results, 
except  when  otherwise  stated,  refer  to  the  behavior  of  one  grain  of 
the  solution. 

1.  Platinic  Chloride. 

This  reagent  throws  down  from  somewhat  strong  aqueous  solu- 
tions of  nicotine  and  of  its  salts  a  yellow  precipitate  of  the  double 
chloride  of  platinum  and  nicotine,  having,  according  to  Ortigosa,  the 
composition  CioHi^N2,2HCl;  PtCl^.  The  precipitate  produced  from 
aqueous  solutions  of  the  free  alkaloid  by  the  pure  reagent  is  at  first 
amorphous,  but  after  a  little  time  it  becomes,  in  part  at  least,  crystal- 
line. But  when  from  solutions  of  the  hydrochloride  of  nicotine,  or 
if  the  reagent  contains  free  hydrochloric  acid,  the  precipitate  immedi- 
ately assumes  the  crystalline  form.  From  more  dilute  solutions  of 
the  alkaloid  or  of  its  salts  the  precipitate  separates  only  after  a  time, 
and  then  in  the  crystalline  state;  its  separation  is  much  facilitated 


442  .  NICOTINE. 

by  stirring  the  mixture.  The  precipitate,  in  its  crystalline  form,  dis- 
solves but  slowly  in  large  excess  of  hydrochloric  acid ;  in  its  amor- 
phous condition,  however,  it  is  much  more  readily  soluble.  It  is 
insoluble  in  acetic  acid,  in  alcohol,  and  in  ether,  but  soluble  in  excess 
of  free  nicotine.     The  crystals  are  permanent  in  the  air. 

1.  y^  grain  of  nicotine,  in  one  grain  of  water,  yields  with  the  re- 

agent a  quite  good  deposit  of  orange-yellow  crystals,  Plate  VI., 

2.  -^^  grain :  after  a  little  time  the  mixture  becomes  turbid,  and 

ultimately  yields  small  crystals  of  the  double  salt.     If  the  mix- 
ture be  stirred  with  a  glass  rod,  it  very  soon  yields  granular 
streaks  on  the  dish  or  glass-slide  over  the  path  of  the  rod,  and 
in  a  little  time  a  quite  satisfactory  crystalline  deposit. 
Platinic  chloride  also  produces  yellow  crystalline  precipitates  in 
solutions  of  potassium  hydrate  and  of  ammonia ;  but  the  forms  of 
the  crystals  thus  produced  are  wholly  different  from  those  of  the 
double  nicotine  salt.    (Compare  Plate  I.,  fig.  1.)    The  application  of 
some  of  the  tests,  such  as  the  iodine  reagent,  which  produce  precipi- 
tates with  nicotine  but  none  with  the  inorganic  alkalies,  would  also 
readily  distinguish  the  former  from  the  latter.    If  the  solution  under 
examination  has  been  prepared  by  extraction  from  a  suspected  mix- 
ture by  chloroform  or  ether,  then   a   mineral  alkali  could   not  be 
present,  since  they  are  insoluble  in  these  liquids. 

This  reagent  also  throws  down  yellow  precipitates  from  solutions 
of  most  of  the  other  alkaloids,  some  of  which,  like  the  nicotine 
deposit,  are  crystalline  ;  but  in  no  instance  have  the  crystals  the 
same  microscopic  forms  as  those  obtained  from  somewhat  strong 
solutions  of  nicotine.  The  production  of  this  crystalline  precipitate, 
together  with  the  odor  and  physical  state  of  nicotine,  readily  serves 
to  distinguish  this  alkaloid  from  all  other  substances. 

2.  Mercuric  Chloride. 

Mercuric  chloride,  or  corrosive  sublimate,  produces  in  strong 
solutions  of  nicotine  a  copious,  white,  curdy  precipitate,  which  soon 
acquires  a  yellow  color  and  deposits  beautiful  groups  of  colorless 
crystals,  which  are  permanent  in  the  air.  The  precipitate  produced 
from  somewhat  dilute  solutions  of  the  alkaloid  remains  white,  and 
after  a  time  yields  the  same  crystals  as  from  strong  solutions.  These 
precipitates  are  readily  soluble  in  hydrochloric  and  acetic  acids.    The 


MERCURIC   CHLORIDE   TEST.  443 

white  precipitate  is  soluble  in  ammonium  chloride,  from  which,  after 
a  time,  it  is  redej)ositc(l ;  the  yellow  precipitate  is  immediately  de- 
colorized by  ammonium  chloride  and,  in  part  at  least,  dissolved,  but 
after  a  time  it  separates  in  the  form  of  a  white  powder.  The  pre- 
cipitates are  to  a  greater  or  less  extent  dissolved  upon  the  application 
of  heat,  but  again  rejiroduced  as  the  solution  cools. 

1.  y^J-jj  grain  of  nicotine,  in  one   grain  of  water,  yields  a  copious, 

white  precipitate,  which  in  a  little  time  becomes  yellow  and 
yields  a  mass  of  large  groups  of  crystals,  Plate  VI.,  fig.  2. 
These  crystals  are  especially  beautiful  under  polarized  light. 

2.  3^  grain  yields  a  rather  copious,  dirty-white  precipitate,  which 

soon  deposits  colorless  crystals. 

3.  Y^jVij"  grain  J  in  a  few  seconds  the  mixture  becomes  turbid,  and 

soon  there  is  a  quite  good,  white,  flocculent  precipitate,  which 
after  a  time  yields  crystals  having  the  same  forms  as  illustrated 
above.  If  upon  the  addition  of  the  reagent  the  mixture  be 
stirred  with  a  glass  rod,  it  immediately  yields  streaks  on  the 
bottom  of  the  watch-glass  over  the  path  of  the  rod,  and  soon  in- 
numerable opaque  granules  and  granular  masses  appear,  which 
after  a  little  time  present  the  appearances  illustrated  in  the 
lower  portion  of  the  above  figure. 

4.  YT^i)  gi'aiii :  if  the  mixture  be  stirred  and  allowed  to  stand,  it  yields 

after  some  time  quite  a  number  of  large  crystalline  groups. 

Although  corrosive  sublimate  also  produces  white  precipitates 
with  ammonia  and  various  inorganic  substances,  as  well  as  with  most 
of  the  alkaloids  and  many  other  kinds  of  organic  matter,  yet  all 
these  deposits,  unlike  that  from  nicotine,  remain  amorphous,  except 
the  precipitate  from  strychnine,  and  in  this  case  the  crystals,  which 
are  usually  obtained  with  difficulty,  are  always  of  a  wholly  different 
form  from  those  produced  by  the  nicotine  deposit.  (Compare  Plate 
XI.,  fig.  2.)  It  may  be  added  thd,t  the  nicotine  precipitate  is  very 
readily  soluble  in  excess  of  acetic  acid,  whereas  the  strychnine  com- 
pound is  soluble  with  difficulty  in  this  acid. 

We  have  found,  in  repeated  experiments,  that  the  precipitate 
produced  by  this  reagent  from  quite  impure  solutions  of  nicotine 
will  after  a  time  yield  characteristic  crystals,  even  in  the  midst  of 
a  dense  deposit  of  foreign  matter.  Nevertheless,  it  must  be  borne 
in  mind  that  under  these  circumstances  the  precipitate  may  fail  to 
crystallize.      In  applying  this  test  to  somewhat  complex  organic 


444  NICOTINE. 

liquids,  the  precipitate  should  be  stirred  and  allowed  to  stand  for  at 
least  an  hour,  with  the  occasional  addition  of  very  small  quantities 
of  pure  water  to  prevent  the  deposit  becoming  dry,  before  it  is  fully 
concluded  that  crystals  will  not  form. 

This  is  the  most  valuable  test  yet  known  for  the  detection  of 
nicotine  when  in  solution. 

3.  Picric  Acid. 

An  alcoholic  solution  of  picric,  or  carbazotic,  acid,  throws  down 
from  aqueous  solutions  of  nicotine  a  yellow,  amorphous  precipitate, 
which  soon  becomes  a  mass  of  crystalline  tufts.  It  is  necessary  to 
use  large  excess  of  the  reagent,  otherwise  either  no  deposit  will  form, 
or  if  produced  it  will  soon  disappear. 

1.  YFo"  grain  of  nicotine  yields  an   immediate  yellow  or  greenish- 

yellow  precipitate,   which  soon  becomes  a  mass  of  groups  of 
yellow,  crystalline  tufts,  Plate  YI.,  fig.  3. 

2.  iQQQ   grain :    a    rather  copious    precipitate,  which   soon  crystal- 

lizes. 

3.  xo.Wo  grain  yields  a  very  good  crystalline  precipitate. 

4.  4^,Vfo  gi'ain  yields  a  just  perceptible  precipitate. 

This  reagent  also  throws  down  from  sohitions  of  the  inorganic 
alkalies,  and  of  several  of  the  other  alkaloids,  besides  nicotine,  yel- 
low precipitates  which  become  crystalline.  But  by  the  aid  of  the 
microscope  the  crystallized  nicotine  compound  may  generally  be 
readily  distinguished  from  all  of  these  deposits  except  that  produced 
from  very  strong  solutions  of  sodium  hydrate  (Plate  I.,  fig.  6),  which 
'has  frequently  much  the  same  crystalline  form  as  that  assumed  by 
the  nicotine  salt.  Any  doubt  as  to  the  true  nature  of  the  deposit 
may,  of  course,  be  readily  removed  by  the  application  of  other 
reagents. 

This  reagent  will  often  produce  crystals  with  only  the  l-10,000th 
of  a  grain  of  nicotine,  in  one  grain  of  water,  in  the  presence  of  for- 
eign organic  matter.  But  in  mixtures  of  this  kind  the  formation 
of  crystals  is  more  readily  interfered  with  than  in  the  application  of 
the  preceding  reagent. 

4.  Iodine  in  Potassium  Iodide. 

This  reagent  may  be  prepared  by  dissolving  five  parts  of  potas- 
sium iodide  in  one  hundred  parts  of  water,  and  then  adding  two 


AURIC  <'[ir,()Rii)F,   rKs'i'.  445 

|)arts  (tf  pure  iodine.  A  dro])  or  (wo  of  lliis  niixtiirc  (lirows  down 
from  solutions  of  nirotiiu'  luul  of  its  salts  a  rcddisli-hrown,  hrouiiisli- 
yellow,  or  yellowish,  amorphous  precipitate,  its  exact  color  depending 
somewhat  upon  the  strength  of  the  alkaloidal  solution,  and  also  upon 
the  quantity  of  reagent  added.  After  a  little  time  the  precipitate 
may  entirely  disajipear;  hut  it  is  immediately  reproduced  upon  fur- 
ther addition  of  the  reagent.  The  precipitate  is  readily  soluble  in 
potassium  hydrate  and  in  alcohol. 

1.  ^1^  grain  of  nicotine,  in  one  grain  of  water,  yields  a  very  coi)ious 

deposit. 

2.  YxiVir  grJ^'"  :  ^  copious,  reddish-brown  precipitate. 

3.  Yir.VuT  gi'^i"  yields  a  good  reddish-yellow  deposit. 

4.  -^--^^jj-jj-jj-  grain  :  a  quite  distinct  greenish-yellow  precipitate. 
6.  -Bij-.Viro"  gi'ain  :  a  quite  good  turbidity. 

6.  "nJT.xnnr  gi"^iii-  ^  very  obvious  turbidity. 

7,  Y^V.innr  g^'^i^  yields  a  perceptible  cloudiness. 

As  a  solution  of  iodine  in  potassium  iodide  causes  no  precipitate 
in  solutions  of  the  inorganic  alkalies  and  has  its  color  immediately 
discharged  by  them,  it  readily  serves  to  distinguish  nicotine  from 
these  substances.  But,  as  the  reagent  produces  with  most  of  the 
alkaloids  and  many  other  substances  precipitates  similar  to  that  from 
nicotine,  it  has  no  positive  value,  for  the  detection  of  this  alkaloid, 
further  than  to  confirm  the  reactions  of  other  tests. 

From  the  fact  that  the  limit  of  the  reaction  of  this  reagent 
exceeds  that  of  either  of  the  other  tests  for  nicotine,  it  is  obvious 
that  should  this  test  fail  to  produce  a  precipitate,  in  a  solution  sus- 
pected to  contain  nicotine,  it  would  be  fruitless  to  apply  any  of  the 
other  tests  to  the  same  solution,  unless  possibly  there  should  be  some 
substance  present  that  interfered  with  the  reaction  of  this  reagent. 

5.  Aiwio  Chloride. 

Trichloride  of  gold  produces  in  aqueous  solutions  of  nicotine  a 
yellow,  amorphous  precipitate,  which  is  nearly  insoluble  in  acetic 
and  hydrochloric  acids,  but  soluble,  to  a  clear  solution,  in  excess  of 
the  caustic  alkalies. 

1.  y^  grain  of  nicotine  yields  an  immediate,  copious,  yellow  pre- 
cipitate, which  remains  amorphous  J  the  deposit  is  not  entirely 
soluble  in  several  drops  of  strong  acetic  acid.  If  several  grains 
or  more  of  the  nicotine  solution  be  precipitated  by  the  reagent 


446  NICOTINE. 

and  the  mixture  then  heated,  the  precipitate  dissolves  to  a 
beautiful  purple  solution. 

2.  YWoo  grain  yields  a  good,  yellow  deposit,  which  is  slowly  soluble 

in  a  few  drops  of  a  strong  solution  of  potassium  hydrate.  If 
the  precipitate  produced  from  several  grains  of  the  solution  be 
heated  in  the  mixture,  it  dissolves,  and  is  reproduced  unchanged 
as  the  mixture  cools. 

3.  gQ-QQ    grain :    an  immediate   greenish-yellow  precipitate,  which 

soon  increases  to  a  quite  good,  dirty-yellow  deposit ;  the  precip- 
itate is  readily  soluble  in  a  drop  of  potassium  hydrate  solution. 

4.  YO-Qo"  grain  yields  a  good,  yellowish  precipitate,  which  imme- 

diately disappears  upon  the  addition  of  an  alkali. 

5.  YF.Voir  grain :  in  a  few  moments  a  distinct  turbidity,  and  in  a 

little  time  a  quite  satisfactory  precipitate. 

6.  -g-o.Vcro"  gi'ain :  in  a  little  time  the  mixture  becomes  turbid,  and 

soon  there  is  a  quite  distinct  deposit. 
Trichloride  of  gold  also  produces  yellow,  amorphous  precipitates 
with  most  of  the  alkaloids  and  various  other  substances. 

6.  Bromine  in  Bromohydrio  Acid. 

Aqueous  solutions  of  nicotine  yield  with  a  strong  aqueous  solu- 
tion of  bromohydric  acid  saturated  with  bromine  a  yellow,  amor- 
phous precipitate,  which  in  a  little  time  disappears. 

1.  yi-g-  grain  of  nicotine  yields  a  copious,  bright  yellow  precipitate, 

which  soon  disappears,  but  is  reproduced  upon  further  addition 
of  the  reagent. 

2.  YFoo"  gi^ain  :  a  rather  copious  precipitate. 

3.  5-^00"  gi^ain  yields  a  very  good,  greenish-yellov/  deposit,  which 

soon  dissolves,  and  is  not  reproduced  upon  further  addition  of 
the  reagent. 

4.  i-o.^-Q^  grain  yields  a  slight  turbidity. 

The  reaction  of  this  reagent  is  common  to  most  of  the  alkaloids 
and  many  other  organic  compounds.  The  reagent  produces  no  pre- 
cipitate and  has  its  color  discharged  when  added  to  solutions  of  the 
caustic  alkalies. 

7.  Tannic  Acid. 

Tannic  acid  produces  in  aqueous  solutions  of  nicotine  a  white, 
amorphous  precipitate,  which  readily  dissolves  to  a  clear  solution  on 


SEPARATION  FROM  ORGANIC  MIXTURES.         447 

the  additioii  of  a  small  (i.iantity  of  hydrochloric  acid,  but  is  repro- 
duced upon  further  addition  of  the  acid,  and  is  then  insoluble  in 
lar<re  excess.  The  precipitate  is  remlily  soluble  in  acetic  and  nitric 
acids,  without  being  reproduced  upon  further  addition  of  the  aci(l. 

1.  ^  grain  of  nicotine,  in    one   grain  of  water,  yields  a  copious 

precipitate. 

2.  ^i^^  grain  :  a  good,  bluish-white  deposit. 

3.  y^^j-g-jy  grain  :  the  mixture  becomes  slightly  turbid. 

This  reagent  also  throws  down  white  precipitates  from  solu- 
tions of  very^many  other  substances.  The  behavior  of  the  nicotine 
precipitate  with  hydrochloric  acid,  however,  is  somewhat  peculiar. 

Other  Reactions  of  Nicotvne.—As  nicotine  has  strong  basic  prop- 
erties, it,  like  the  caustic  alkalies,  precipitates  the  oxides  of  many 
of  the  metals  from  solutions  of  their  salts.  Mercurous  nitrate  throws 
down  from  somewhat  strong  solutions  of  the  free  alkaloid  a  copious, 
dirty-yellow  precipitate,  which  almost  immediately  becomes  brown, 
then  nearly  black :  this  transition  of  color  is  due  to  the  successive 
reduction  of  the  precipitated  oxide  of  mercury.  With  one  grain  of 
a  l-5000th  solution  of  the  alkaloid  this  reagent  produces  a  rather 
good,  dirty-white  precipitate. 

Sulphate  of  copper  produces  with  aqueous  solutions  of  the  alka- 
loid, when  not  too  dilute,  a  bluish,  flocculent  precipitate  of  the  oxide 
of  copper,  which  is  insoluble  in  excess  of  nicotine.  The  statement 
of  some  writers  that  this  precipitate  dissolves  in  excess  of  the  pure 
alkaloid  to  a  blue  solution,  similar  to  that  formed  by  ammonia,  is 
certainly  erroneous.  Solutions  of  salts  of  lead,  silver,  nickel,  cobalt, 
and  several  other  metals  also  produce  precipitates  from  somewhat 
strong  solutions  of  the  alkaloid.  A  1-1 00th  solution  of  nicotine 
yields  with  silver  nitrate  a  quite  good,  white  precipitate,  which  but 
very  slowly  darkens  upon  exposure  to  sunlight. 

Solutions  of  nicotine,  even  when  concentrated,  fail  to  yield  a 
precipitate  with  either  potassium  sulphocyanide,  the  chromates  of 
potassium,  ferro-  or  ferri-cyanide  of  potassium,  or  gallic  acid. 

Separation  from  Organic  Mixtures. 
In  suspected   poisoning   by  tobacco,  before   proceeding  to  the 
chemical  examination  for  nicotine,  the  analyst  should  carefully  ex- 
amine the  suspected   mixture  or  contents  of  the  stomach  for  the 


448  NICOTINE. 

presence  of  tobacco  in  its  solid  state.  Any  portions  of  the  plant 
thus  found,  separated  from  all  adhering  matter,  should  be  carefully 
examined,  by  means  of  the  microscope  if  necessary,  in  regard  to  their 
botanical  characters,  then  digested  at  a  gentle  heat  in  acidulated  water, 
and  the  solution  examined  in  the  manner  just  to  be  described. 

Suspected  Solutions  and  Contents  of  the  Stomach. — The  mixture 
submitted  for  examination,  diluted  with  distilled  water  if  necessary, 
is  slightly  acidulated  with  acetic  acid  and  digested  for  some  little 
time  at  a  moderate  heat ;  it  is  then  allowed  to  cool,  the  liquid  strained 
through  muslin,  the  solids  on  the  muslin  washed  with  water  and  well 
pressed,  and  the  united  strained  liquids  filtered.  The  clear  liquid  is 
now  evaporated  to  a  small  volume  on  a  water-bath,  then  mixed  with 
about  an  equal  volume  of  strong  alcohol,  and  the  mixture  gently 
warmed  for  some  minutes  with  constant  stirring ;  the  cooled  liquid 
is  again  filtered,  and  the  filtrate  evaporated  on  a  water-bath  to  very 
near  dryness.  Any  nicotine  originally  present  will  now  be  in  the 
residue  in  the  form  of  acetate  of  the  alkaloid. 

This  residue  is  gently  warmed  with  about  a  fluid-drachm  or  even 
less  of  pure  water,  the  mixture  thoroughly  stirred,  transferred  to  a 
wet  paper  filter,  and  the  filtrate  collected  in  a  stout  test-tube.  Tiie 
contents  of  the  tube  are  now  rendered  alkaline  by  a  few  drops  of 
potassium  or  sodium  hydrate,  when  the  nicotine  will  be  liberated 
from  its  saline  combination,  and  perhaps  emit  its  peculiar  odor. 

The  mixture  is  now  violently  shaken  for  some  minutes  with  about 
two  volumes  of  chloi'oform  or  about  five  volumes  of  ether,  and  this 
mixture  allowed  to  repose  until  the  fluids  have  completely  separated. 
In  case  chloroform  has  been  used  as  the  solvent  of  the  liberated  alka- 
loid, the  supernatant  aqueous  fluid  is  removed  by  means  of  a  pipette, 
the  chloroform  carefully  decanted  into  another  perfectly  dry  test-tube, 
and  from  this  into  a  large  watch-glass.  By  these  decantations,  any 
globules  of  water  which  may  have  escaped  removal  by  the  pipette 
may,  by  care,  be  made  to  adhere  to  the  sides  of  one  or  other  of  the 
test-tubes.  Should,  however,  globules  of  the  alkaline  aqueous  fluid 
have  passed  along  with  the  chloroform  into  the  watch-glass,  these  must 
be  removed  before  the  latter  liquid  is  evaporated  to  dryness,  other- 
wise the  residue  will  contain  a  trace  of  the  fixed  alkali,  which  might 
subsequently  interfere  with  some  of  the  tests  for  nicotine.  The 
alkaline  aqueous  liquid  removed  by  the  pipette  is  now  washed  with 
something  less  than  its  own  volume  of  fresh  chloroform,  and  this,  after 


SEPARATION  FROM  ORGANIC  MIXTURES.         449 

repose,  decanted  and  added  to  the  first  chloroform  extract.  If  ether 
has  been  emph)yed  as  the  solvent  of  the  alkaloid,  the  aqueous  fluid 
is  ajxitated  a  second  time  with  two  or  three  volumes  of  ether,  and 
the  united  ethereal  liquids  carefully  collected  in  a  large  watch-glass. 

The  contents  of  the  watch-glass  are  now  allowed  to  evaporate 
spontaneously,  in  a  cool  j)]ace,  when  any  nicotine  present  will  be  left 
in  the  form  of  oily  drops  or  streaks,  having  the  peculiar  odor  of  the 
alkaloid,  especially  upon  the  application  of  a  very  gentle  heat.  As 
•the  residue  from  extracts  of  this  kind  has  frequently  a  strong  animal 
odor,  this  may  more  or  less  conceal  that  of  the  poison. 

If  the  residue  thus  obtained  indicates  the  presence  of  a  compara- 
tively large  quantity  of  the  alkaloid,  the  contents  of  the  watch-glass 
are  stirred  with  about  half  a  drachm  or  more  of  pure  water,  and  the 
mixture,  if  it  contains  white,  flocculent  masses,  or  if  turbid,  trans- 
ferred in  small  portions  to  a  very  small  moistened  filter  :  when  the 
whole  of  the  fluid  has  passed  through,  the  filter  is  washed  with  a  few 
dro})s  of  water  and  this  collected  with  the  first  filtrate.  If,  on  the 
other  hand,  the  chloroform  residue  fails  to  reveal  any  distinct  evi- 
dence of  the  presence  of  the  alkaloid,  only  a  few  drops  of  water  are 
used  for  its  solution. 

A  drop  of  the  clear  liquid,  transferred  by  means  of  a  pipette  to 
a  watch-glass,  may  now  be  treated  with  a  small  drop  of  corrosive 
sublimate  solution,  the  mixture  allowed  to  stand  quietly  for  some 
little  time,  and  then  examined  by  the  microscope.  If  this  examina- 
tion indicates  the  presence  of  nicotine,  other  portions  of  the  clear 
liquid  may  be  examined  by  platinic  chloride,  picric  acid,  and  any  of 
the  other  tests  for  this  alkaloid.  If,  however,  the  corrosive  sublimate 
mixture  fails  to  yield  crystals,  it  should  be  stirred  with  a  glass  rod, 
and  allowed  to  stand  half  an  hour  or  longer.  Should  it  still  fail  to 
yield  any  evidence  of  the  presence  of  the  poison,  the  original  liquid 
may  be  concentrated,  and  then  a  drop  examined  by  this  reagent.  On 
the  other  hand,  should  this  test  as  first  applied  indicate  the  pres- 
ence of  much  foreign  matter,  the  original  solution  is  again  extracted 
by  chloroform,  this  liquid  evaporated  to  dryness,  and  the  residue 
treated  as  before. 

By  the  method  now  considered,  nicotine  was  detected  in  very 
notable  quantities  in  the  stomachs  of  the  first  two  cats  before  referred 
to  {ante,  437),  each  of  which  was  killed  by  a  single  drop  of  the  al- 
kaloid placed  in  the  mouth  of  the  animal.     And  by  it  we  have  also 

29 


450  NICOTINE. 

obtained  perfectly  satisfactory  evidence  of  the  presence  of  the  poison 
in  an  ounce  of  a  very  complex  organic  mixture,  to  which  only  the 
1-lOOth  of  a  grain  of  the  alkaloid  had  been  added. 

From  the  Tissues. — For  the  separation  of  absorbed  nicotine  from 
the  tissues,  the  solid  organ,  such  as  the  liver,  spleen,  or  lungs,  is  cut 
into  very  small  shreds,  then  made  into  a  thin  paste  with  water,  the 
mixture  acidulated  with  acetic  acid,  and  digested,  with  frequent  stir- 
ring, for  some  time  at  a  very  gentle  heat.  The  cooled  mixture  is 
then  treated  in  the  same  manner  as  before  described  for  the  examina- 
tion of  suspected  solutions. 

As  the  quantity  of  the  alkaloid  present  in  the  tissues,  in  poison- 
ing by  this  substance,  is  at  most  extremely  small,  the  residue  obtained 
from  the  chloroform  extract  should  be  treated  with  only  a  few  drops 
of  water,  and  great  care  exercised  in  the  preparation  of  this  solution 
for  the  application  of  the  different  tests. 

M.  Stas  was,  perhaps,  the  first  to  show  that  nicotine  was  absorbed 
and  might  be  separated  from  the  tissues  in  its  unchanged  state.  The 
same  fact  was  also  pointed  out  about  the  same  time  by  Orfila.  This 
observer  cites  several  instances  [Toxicologie,  1852,  ii.  493)  in  which 
he  obtained  the  poison  from  the  liver  and  spleen  of  dogs  killed  by 
from  fifteen  to  twenty  drops  of  the  alkaloid. 

From  the  Blood. — Nicotine,  when  present  in  the  blood,  may  be 
recovered  by  acidulating  the  liquid  with  about  five  drops  of  strong 
acetic  acid  for  each  ounce  of  fluid,  and  agitating  it  in  a  closed  bottle 
with  about  its  own  volume  or  more  of  a  mixture  of  equal  parts  of 
water  and  alcohol,  until  the  whole  becomes  perfectly  homogeneous. 
The  mixture  is  then  digested  at  a  moderate  heat,  with  frequent  stir- 
ring, until  the  albuminous  matter  present  collects  into  small  brown- 
ish flakes.  The  cooled  liquid  is  strained  through  wet  muslin,  and 
the  solid  residue  washed  and  strongly  pressed.  If  the  liquid  is  still 
turbid,  it  is  passed  through  the  strainer  a  second  or  even  a  third  time. 
The  fluid  is  now  evaporated  at  a  moderate  heat  on  a  water-bath 
to  about  half  its  volume,  and  while  still  warm  mixed  with  a  little 
strong  alcohol,  and  the  reddish-brown,  coagulated  matter  removed  by 
a  muslin  filter.  When  the  quantity  of  blood  operated  upon  is  com- 
paratively small,  the  strained  liquid  thus  obtained  is  usually  clear  and 
has  only  a  slight  yellow  color ;  but  when  a  large  amount  of  the  fluid 
is  examined,  the  strained  liquid  is  generally  turbid  and  highly  colored. 
Under  these  circumstances  it  may  be  passed  through  a  wet  paper  filter. 


RECOVERY    FUOM    THE    RLOOD.  461 

Tlie  Ii((iii(l  is  now  slowly  evaporated  on  a  water-bath  to  near 
dryness.  If  (ImiiiL;-  tlio  concentration  much  solid  matter  separates, 
it  should  bo  removed  by  a  small  filter.  The  nearly  dry  residue  is 
stirred  with  about  half  a  dracrhm  of  water,  the  solution  filtered,  the 
filtrate  rendered  alkaline  by  sodium  hydrate,  and  extracted  by  chloro- 
form in  the  usual  manner.  The  chloroform  residue  is  well  stirred 
with  a  few  drops  of  water,  and  the  liquid  carefully  separated  from 
any  flakes  of  animal  matter  present,  either  by  means  of  a  pipette  or 
by  a  very  small  filter.  The  liquid  is  then  examined  by  the  ordinary 
reagents. 

By  the  above  method,  perfectly  satisfactory  evidence  of  the  pres- 
ence of  nicotine  was  obtained  from  one  ounce  of  healthy  blood  to 
which  the  1-lOOth  of  a  grain  of  the  alkaloid  had  been  purposely 
added, — the  dilution  being  one  part  of  the  poison  in  about  50,000 
parts  of  the  fluid. 

In  the  case  of  the  second  of  the  three  cats  before  referred  to, — in 
which  a  small  drop  of  nicotine  proved  fatal  in  two  minutes  and  a 
half, — seven  fluid-drachms  of  blood  were  recovered  from  the  body 
immediately  after  death ;  five  drachms  of  the  liquid  were  then  treated 
after  the  above  method,  and  the  final  aqueous  solution  reduced  to 
three  drops.  One  drop  of  this  mixture,  when  treated  with  corrosive 
sublimate,  gave  after  a  little  time  perfectly  satisfactory  evidence  of 
the  presence  of  nicotine,  it  yielding  about  twenty  large  groups  of 
crystals  similar  to  those  shown  in  Plate  VI.,  fig.  2.  A  second  drop, 
treated  with  picric  acid,  also  furnished  a  fine  deposit  of  characteristic 
crystals.  The  third  drop  gave  with  platinic  chloride  a  slight  precipi- 
tate, but  no  crystals  were  obtained. 

From  the  third  cat — which  was  killed  in  seventy-jive  seconds  by 
a  drop  of  the  alkaloid — ten  fluid-drachms  of  blood  were  obtained 
with  the  greatest  possible  speed  and  care,  and  then  treated  as 
before  described,  except  that  a  drop  of  sulphuric  acid  was  used  as 
the  acidifying  agent,  and  ether  for  the  extraction  of  the  poison. 
The  final  solution,  when  reduced  to  two  drops,  gave  with  corrosive 
sublimate  and  picric  acid  perfectly  satisfactory  evidence  of  the  pres- 
ence of  the  alkaloid,  but  at  the  same  time  indicated  that  it  was 
present  in  smaller  quantity  than  in  the  preceding  case.  This  case 
shows  the  extreme  rapidity  with  which  this  poison  may  enter  the 
circulation. 

It  is  a  singular  fact  that  the  chloroform  and  ether  residues  in 


452  NICOTINE. 

both  the  foregoing  cases  possessed  in  a  very  marked  degree  the 
peculiar  ethereal  odor  of  the  pure  alkaloid  administered ;  whilst  in 
another  case,  in  which  the  poisoning  was  occasioned  by  an  extract 
of  tobacco,  the  chloroform  residue  obtained  in  precisely  the  same 
manner  had  the  acrid  tobacco  odor  usually  observed  in  commercial 
samples  of  nicotine. 

In  the  examination  of  organic  mixtures  for  the  separation  of 
nicotine  it  has  heretofore  been  usual  for  analysts  to  advise  either 
oxalic,  tartaric,  or  sulphuric  acid  as  the  acidifying  agent.  But  we 
have  not  found  that  either  of  these  acids  possesses  for  this  purpose 
any  advantage  over  acetic  acid,  and,  on  the  whole,  prefer  the  latter. 
If  sulphuric  acid  be  employed,  no  more  should  be  added  than  just 
sufficient  to  give  the  mixture  a  very  slight  acid  reaction.  It  may 
here  be  remarked  that  anhydrous  acetate  of  nicotine  is  more  or  less 
volatilized  by  continued  heating  on  a  water-bath ;  and,  also,  that  this 
salt  is  soluble  to  a  notable  extent  in  ether. 

For  the  separation  of  the  liquid  alkaloids,  nicotine  and  conine, 
from  organic  mixtures,  the  following  method,  based  upon  the  vola- 
tility of  these  alkaloids,  has  been  proposed.  The  mixture,  acidified 
with  from  ten  to  twenty  grains  of  oxalic  or  tartaric  acid,  is  treated 
with  about  twice  its  weight  of  strong  alcohol  and  heated  to  about 
66°  C.  (150°  F.),  the  cooled  liquid  strained,  the  residue  washed  with 
alcohol  and  pressed.  The  extract  thus  obtained  is  concentrated  at 
a  gentle  heat,  the  resulting  aqueous  solution  separated  by  filtration 
from  any  insoluble  matter  present,  then  rendered  alkaline  by  potas- 
sium or  sodium  hydrate,  and  distilled  to  very  near  dryness  in  a  retort 
provided  with  a  proper  receiver :  the  residue  in  the  retort  may  be 
treated  with  a  little  water  and  again  distilled,  the  product  being 
received  with  the  first  distillate.  The  alkaloid  will  now  be  present 
in  the  distillate. 

This  liquid  may  either  be  agitated  with  several  volumes  of  ether, 
the  ethereal  solution  decanted,  and  the  operation  repeated  with  fresh 
portions  of  ether  until  a  drop  of  this  fluid  upon  spontaneous  evapo- 
ration no  longer  leaves  a  residue  of  the  alkaloid ;  the  mixed  ethereal 
liquids  are  then  evaporated  spontaneously  at  a  low  temperature,  and 
the  residue  placed  for  a  few  moments  over  sulphuric  acid  under  a 
glass  receiver.  Or,  the  distillate  may  be  neutralized  with  oxalic 
acid,  concentrated   at  a   low   temperature  to   a   small  volume,  the 


CONINE.  453 

residual  liquid  rendered  alkaline  by  potassium  or  sodium  hydrate, 
and  the  alkaloid  then  extracted  by  ether.  Chloroform  might,  of 
course,  be  substituted  for  ether  in  either  of  these  processes. 

Since  this  method,  by  distillation,  is  always  attended  with  a  quite 
notable  loss  of  the  alkaloid,  it  is  not  as  well  adapted  for  the  detec- 
tion of  very  minute  quantities  of  the  poison  as  the  method  before 
considered. 

Section  II. — Conine.     (Conium  Maculatum.) 

Histori/. —  Conine,  known  also  as  conic'me,  conia,  and  conicina,  is 
the  active  principle  of  Conium  maculatum,  or  common  hemlock.  It 
exists,  in  the  form  of  an  organic  salt,  perhaps  in  all  parts  of  the 
plant,  but  is  most  abundant  in  the  fruit.  The  relative  quantity  of 
the  alkaloid  present  in  the  plant  varies  with  the  growth  of  the  latter: 
according  to  Geiger,  seventy-two  parts  of  the  fresh,  green,  unripe 
seeds,  or  one  hundred  and  eight  parts  of  dry,  ripe  seeds,  yield  one  part 
of  conine.  This  alkaloid  was  first  obtained  as  an  impure  sulphate 
by  Giseke,  in  1827;  Geiger,  in  1831,  obtained  it  in  its  pure  state,  and 
described  some  of  its  properties  and  effects  upon  animals.  Its  effects 
upon  animals  were  more  fully  examined,  in  1835,  by  Dr.  Christi.son. 
Various  formulae  have  been  assigned  to  conine; -but  according  to 
Gei-hardt  it  has  the  composition  CgHi^N.  More  recently,  however, 
Prof.  A.  W.  Hofmann,  of  Berlin,  has  concluded  {Ber.  d.  Deut.  Chem. 
Ges.,  1881,  705)  that  its  composition  is  CgHj^N. 

Preparation. — Conine  may  be  obtained,  according  to  Dr.  Chris- 
tison,  by  exhausting  the  ripe  seeds  of  hemlock  with  alcohol,  distil- 
ling off  the  alcohol,  mixing  the  residual  syrup  with  an  equal  volume 
of  water  and  a  little  potassium  hydrate,  distilling  the  mixture  in 
a  chloride  of  calcium  bath,  and  collecting  the  distillate  in  a  proper 
receiver.  The  conine  passes  over  with  the  water  and  yields  an 
aqueous  solution  of  the  alkaloid,  containing  oily  drops  floating  upon 
its  surface.  If  the  conine  contains  ammonia,  this  may  be  removed 
by  placing  the  mixture  in  vacuo  over  sulphuric  acid,  when  the  gas 
will  escape  in  the  form  of  bubbles. 

J.  Schorm  has  proposed  to  exhaust  the  seeds  with  water  acidulated 
with  acetic  acid,  and  evaporate  the  extract  in  a  vacuum  to  the  con- 
sistence of  a  syrup.  Magnesia  is  then  added  to  the  product,  and  the 
whole  agitated  with  ether,  which  will  extract  the  alkaloid  in  its  pure 
state.    {Amer.  Jour.  Pharm.,  July,  1882,  359.) 


454  CONINE. 

Some  years  since  (1871),  H.  Schiff  announced  that  he  had  suc- 
ceeded in  preparing  conine  artificially  ;  but  subsequent  examinations 
proved  that  the  substance  thus  produced  was  merely  isomeric  but  not 
identical  with  conine. 

Conine  is  a  most  virulent  poison,  almost  equalling  in  the  activity 
of  its  action  hydrocyanic  acid.  As  yet  there  seems  to  be  only  a 
single  recorded  case  of  poisoning  in  the  human  subject  by  this  sub- 
stance in  its  pure  state  [Arch,  der  Pharm.,  Sept.  1861,  257);  but 
poisoning  by  hemlock  is  of  not  unfrequent  occurrence.  Most  of 
these  cases  have  resulted  from  the  mistaking  of  hemlock  for  other 
plants. 

Symptoms. — The  symptoms  occasioned  by  hemlock  are  subject 
to  considerable  variation,  as  may  be  seen  from  the  following  cases. 
In  an  instance  related  by  Dr.  Haaf,  a  soldier,  having  eaten  some  soup 
containing  hemlock  leaves,  soon  fell  asleep :  in  an  hour  and  a  half 
afterward  he  was  insensible  and  breathed  with  difficulty ;  his  pulse 
was  slow  and  hard ;  the  extremities  cold ;  and  the  face  bluish  and 
distended  with  blood,  like  that  of  a  person  strangulated.  An  emetic 
of  tartarized  antimony  was  then  administered,  but  it  only  produced 
vain  efforts  to  vomit.  He  complained  of  being  cold,  and  soon  again 
lost  the  power  of  speech  and  consciousness,  and  died  in  about  three 
hours  after  taking  the  poison.  [Orjila^s  Toxicology,  ii.  537.)  In  a 
case  quoted  by  Dr.  A.  Stille  [Mat  Med.,  ii.  268),  a  man,  who  took 
ten  drachms  of  an  extract  of  hemlock,  experienced  great  restlessness 
and  anxiety,  dropped  insensible  from  his  chair,  had  convulsions,  and 
expired  in  two  hours  after  taking  the  dose.  Dr.  Christison  relates  a 
case  (op.  cit.,  657)  in  which  an  old  woman  swallowed  two  ounces 
of  a  strong  infusion  of  hemlock  leaves  with  the  same  quantity  of 
whiskey,  and  died  an  hour  afterward,  comotose  and  convulsed. 

The  following  case  is  reported  by  Dr.  J.  H.  Bennett.  [Edin.  Med. 
and  Surg.  Jour.,  July,  1845,  169.)  A  man  ate  a  large  quantity  of 
hemlock,  believing  it  to  be  parsley.  He  soon  afterward  lost  the 
power  of  walking,  staggered,  and  finally  fell,  but  still  retained  his 
consciousness  and  intelligence.  In  about  two  hours  after  taking  the 
poison  there  was  complete  paralysis  of  the  upper  and  lower  extremi- 
ties, with  occasional  spasmodic  movements  of  the  left  leg ;  and  the 
patient  had  lost  the  power  of  sight,  deglutition,  and  speech,  but  was 
still  sensible :  his  pulse  and  breathing  were  natural.  The  pupils 
became  fixed,  the  action  of  the  heart  very  feeble,  and  death  ensued 


PHY8IOLOGICAI.    EFFECTS.  455 

in  about  tlirei'  hours  and  a  quarter  after  the  poison  had  been  taken. 
In  a  case  quoteil  by  Dr.  Pereira  {Mat.  Med.,  ii.  732),  an  overdose  of 
this  phuit  also  produced  <i;cueral  ])aralysis:  the  under  jaw  fell,  the 
saliva  ran  from  the  mouth,  the  uriue  dropped  from  the  bladder,  and 
the  contents  of  the  rectum  were  discharged.  The  patient  continued 
for  nearly  an  hour  in  this  condition,  unaijle  to  move  or  to  command 
the  sliijhtest  muscular  exertion,  thou<j;h  all  the  time  perfectly  sensible; 
but  under  the  use  of  stimulants  he  finally  recovered. 

Conine,  when  administered  in  its  pure  state,  according  to  the 
experiments  of  Dr.  Christison,  acts  at  first  as  a  local  irritant;  but 
its  local  effects  are  quickly  followed  by  general  palsy  of  the  muscles, 
affecting  first  those  of  voluntary  motion,  then  the  respiratory  muscles 
of  the  chest  and  abdomen,  and  lastly  the  diaphragm,  ending  in  death 
by  asphyxia.  In  some  cases  convulsive  tremors  were  observed. 
The  heart  continued  to  pulsate  after  other  signs  of  life  had  ceased. 
In  no  case  did  the  external  senses  seem  to  be  affected  until  respira- 
tion was  impaired.  This  observer  states  that  a  single  drop  of  the 
alkaloid  applied  to  the  eye  of  a  rabbit  killed  it  in  nine  minutes; 
and  three  drops,  applied  in  the  same  manner,  killed  a  strong  cat  in 
a  minute  and  a  half.  Five  drops,  introduced  into  the  throat  of  a 
small  dog,  began  to  act  in  thirty  seconds,  and  proved  fatal  in  one 
minute;  and  two  grains  of  the  hydrochloride,  injected  into  the 
femoral  vein  of  a  young  dog,  killed  it  before  there  was  time  to 
note  the  interval.     {On  Poisons,  655.) 

The  following  results  were  observed  in  some  of  our  own  experi- 
ments with  the  pure  alkaloid.  A  single  drop  of  the  alkaloid  was 
placed  upon  the  tongue  of  a  large  and  healthy  cat.  In  a  few  seconds 
the  animal  was  inclined  to  stand  still,  and  manifested  an  unsteady 
gait  when  disturbed  ;  in  two  minutes  and  a  half  it  fell  on  its  right 
side,  then  voided  urine,  had  violent  convulsive  movements  of  the 
limbs,  and  a  tremulous  motion  of  all  parts  of  the  body,  and  was 
dead  in  three  minutes  after  the  poison  had  been  administered.  In 
another  experiment,  the  animal,  being  immediately  placed  upon  its 
feet,  stood  perfectly  still,  and  the  pupils  of  the  eyes  became  dilated 
and  insensible  ;  in  forty-five  seconds  the  legs  of  the  animal  became 
powerless,  and  it  sank  upon  its  abdomen,  then  passed  urine,  had 
violent  spasms  of  the  extremities,  and  died  in  four  minutes  after  the 
exhibition  of  the  poison. 

Treatment. — The  treatment  in  poisoning  by  hemlock  is  much 


456  CONINE. 

the  same  as  that  already  pointed  out  for  an  overdose  of  tobacco 
{ante,  p.  438).  As  an  emetic,  mustard  has  been  strongly  advised. 
Dr.  Pereira  was  of  the  opinion  that  strychnine  might  be  found 
beneficial,  on  account  of  its  opposite  physiological  effects  to  those  of 
conine. 

Post-mortem  Appearances. — There  is  generally  more  or  less 
venous  congestion,  especially  in  the  brain,  and  a  fluid  condition  of 
the  blood.  In  the  case  reported  by  Dr.  Haaf,  the  stomach  was  found 
half  filled  with  undigested  matters,  and  there  were  some  red  spots 
around  the  pylorus.  The  intestines  were  natural,  and  the  vena 
cava  and  heart  empty,  but  all  the  vessels  of  the  brain  were  highly 
gorged  with  liquid  blood.  In  the  case  examined  by  Dr.  Christison, 
in  which  death  took  place  in  an  hour,  the  vessels  of  the  brain  were 
not  particularly  turgid,  but  the  blood  throughout  the  body  was 
remarkably  fluid. 

In  Dr.  Bennett's  case,  sixty-three  hours  after  death  an  unusual 
quantity  of  fluid  blood  was  found  in  the  vessels  of  the  scalp  and 
in  the  sinuses  of  the  brain ;  with  slight  serous  effusion  beneath  the 
arachnoid  membrane,  and  into  the  ventricles,  and  numerous  bloody 
points  in  the  substance  of  the  brain.  The  lungs  were  gorged  with 
dark-red,  fluid  blood.  The  blood  throughout  the  body  was  of  a  dark 
color  and  fluid.  The  stomach  contained  a  pultaceous  vegetable  mass ; 
and  the  mucous  membrane  was  much  congested,  especially  at  its 
cardiac  extremity.  The  intestines  and  other  viscera  were  healthy,  but 
partially  congested.  On  examining  the  contents  of  the  stomach,  they 
were  found  to  contain  fragments  of  leaves  of  the  Conium  maculatum, 
which  on  being  bruised  in  a  mortar,  with  a  solution  of  caustic  potash, 
evolved  the  peculiar  mousy  odor  of  conine. 

Chemical  Properties. 

General  Chemical  Nature. — Conine,  in  its  perfectly  pure 
state,  is  a  colorless,  transparent,  oily  liquid,  having  a  strong  alka- 
line reaction,  and,  according  to  Blyth,  a  specific  gravity  of  0.87 ;  it 
has  a  peculiar,  repulsive,  and  suffocating  odor,  resembling  some- 
what that  of  a  long-used  tobacco-pipe.  When  the  alkaloid  is  diluted 
with  water  it  emits  an  odor  similar  to  that  of  mice.  This  peculiar 
odor  is  perceptible  even  in  highly  diluted  solutions :  a  few  drops 
of  a  pure  aqueous  solution  containing  only  the  1— 50,000th  of  its 
weight  of  the  free  alkaloid,  when   enclosed  for  a  little  time  in  a 


SPECIAL   CHEMIOAL    PROPERTIES.  457 

small  test-tube,  impart  tlic  odor,  in  a  very  inaiked  degree,  to  tlu; 
contained  air. 

Conine  imparts  a  transient  greasy  stain  to  white  paper,  and  burns 
with  a  l)right,  smoky  flame;  its  taste  is  repulsive  and  persistent.  Its 
boiling  point,  aeeording  to  Th.  Wertheim,  is  163.5°  C.  (326°  F.) ;  but 
it  distils  with  the  vapor  of  water  at  100°  C.  (212  F°.),  with,  however, 
partial  decomposition.  The  more  rapidly  it  is  distilled,  the  less  de- 
composition it  suffers.  When  heated  in  an  atmosphere  of  hydrogen 
gas,  it  may  be  distilled  without  change.  When  preserved  from  the 
action  of  the  air,  it  remains  colorless,  but  upon  ex^josure  it  becomes 
yellow,  then  brownish,  and  it  is  finally  resolved  into  a  brownish  resin 
and  ammonia. 

SolubilUi/. — According  to  Geiger,  with  whose  observation  our  own 
closely  agrees,  conine  dissolves  at  ordinary  temperatures  in  about  one 
hundred  parts  of  pure  water;  its  aqueous  solutions,  when  not  too 
dilute,  have  a  strongly  alkaline  reaction.  When  excess  of  conine  is 
agitated  with  water,  it  divides  into  minute  drops  and  gives  the  mix- 
ture a  milky  appearance  ;  on  repose,  the  excess  of  the  alkaloid  collects 
on  the  surface  of  the  water  as  an  oily  layer.  It  is  very  soluble  in 
alcohol,  in  ether,  and  in  chloroform.  Both  ether  and  chloroform 
readily  separate  the  alkaloid  from  its  aqueous  solutions,  and  upon 
spontaneous  evaporation  leave  it  in  the  form  of  oily  drops;  the 
former  of  these  liquids  separates  conine  from  water  much  more 
readily  than  it  does  nicotine. 

1.  Extraction  by  Ether. — When  a  1-lOOth  aqueous  solution  of 
free  conine  is  agitated  with  five  volumes  of  ether,  and  this  fluid  de- 
canted, the  aqueous  liquid  is  reduced  to  about  a  l-4000th  solution 
of  the  poison.  Under  these  circumstances,  therefore,  ether  extracts 
about  39-40ths  of  the  alkaloid. 

2.  By  Chloroform.- — When  a  1-1 00th  solution  of  the  free  alka- 
loid is  agitated  with  five  volumes  of  chloroform,  the  aqueous  solution 
is  reduced  to  about  the  same  extent  as  when  treated  under  similar 
circumstances  with  ether. 

Special  Chemical  Properties. — Exposed  to  the  vapors  of 
volatile  acids,  conine  gives  rise  to  dense,  white  fumes.  It  neutralizes 
acids  completely,  forming  odorless  salts,  but  few  of  which  have  been 
obtained  in  the  crystalline  state.  The  conine  used  in  the  present 
investigations  was  freshly  prepared,  had  a  just  perceptible  yellowish 
tint,  and  was  perfectly  free  from  ammonia :  at  least  Nessler's  test, 


458  CONINE. 

which  will  indicate  the  presence  of  ammonia  in  a  few  drops  of  a 
l-500.000th  solution  of  the  alkali,  failed  to  indicate  its  presence  in 
a  saturated  aqueous  solution  of  the  alkaloid. 

If  a  drop  of  the  alkaloid  be  placed  in  a  watch-glass  and  covered 
by  an  inverted  watch-glass  containing  a  drop  of  hydrochloric  acid, 
the  glasses  immediately  become  filled  with  dense,  white  fumes,  and 
the  drop  of  conine  very  soon  solidifies  to  a  mass  of  beautiful  crystal- 
line needles,  Plate  VI.,  fig.  4;  after  a  time  similar  crystals  form  in 
the  hydrochloric  acid  drop.  When  diluted  solutions  of  the  alkaloid 
are  exposed  to  the  vapor  of  hydrochloric  acid,  they  also  give  rise  to 
white  fumes,  and  the  conine  solution  when  concentrated  spontaneously 
deposits  crystalline  needles  of  hydrochloride  of  conine,  C8lIi5]S',IICl, 
or,  according  to  Hofmann,  CgH^^NjIICl.  The  same  crystals  are 
obtained  by  neutralizing  an  aqueous  solution  of  the  alkaloid  with  the 
diluted  acid,  and  allowing  the  mixture  to  evaporate  spontaneously. 
The  crystals  are  permanent  in  the  air :  the  statement  of  some  writers 
that  they  are  deliquescent  is  erroneous. 

When  strong  hydrochloric  acid  is  brought  in  contact  with  pure 
conine,  the  mixture  assumes  a  pale  red  color,  which  increases  in  in- 
tensity, and  after  a  time  becomes  nearly  blood-red ;  if  the  mixture  be 
evaporated  spontaneously  to  near  dryness,  it  deposits  a  mass  of  long, 
crystalline  needles,  which  are  readily  soluble  in  water  and  in  alcohol, 
and  redeposited  as  the  liquid  evaporates. 

An  aqueous  solution  of  conine,  when  treated  with  a  saturated 
solution  of  chlorine  gas,  becomes  turbid.  A  drop  of  a  1-lOOth  solu- 
tion yields  in  this  manner  a  dense,  white  turbidity ;  the  same  quan- 
tity of  a  1-lOOOth  solution  yields  after  a  time  a  slight  cloudiness. 

Nitric  acid  exposed  to  the  vapor  of  conine  gives  rise  to  dense, 
white  fumes.  When  the  alkaloid  is  treated  directly  with  excess  of 
the  acid,  it  yields  after  a  little  time  a  pale  red  mixture,  which  after 
a  few  days  becomes  converted  into  a  deep  red  liquid  containing  a 
mass  of  colorless,  crystalline  needles. 

Sulphuric  acid  forms  with  the  pure  alkaloid  a  pale  red  liquid, 
which  after  a  few  days  deposits  crystalline  needles  along  the  margin 
of  the  mixture.  If  a  sulphuric  acid  solution  of  the  alkaloid  or  of 
any  of  its  salts  be  treated  with  a  small  crystal  of  potassium  dichro- 
mate,  the  mixture  upon  being  stirred  slowly  assumes  a  green  color, 
due  to  the  formation  of  sesquioxide  of  chromium. 

Upon  neutralizing  pure  conine  or  its  aqueous  solution  with  oxalic 


AURIC   CHLORIDE   TEST.  459 

acid,  the  inixturo  upon  spontaneous  evaporation  yields  prismatic 
crystals  of  the  oxalate  of  coninc.  If  the  mixture  be  evaporated  in 
a  water-bath,  the  salt  is  left  in  the  form  of  a  gummy  mass. 

Most  of  the  tiCiHs  of  Conine  are  soluble  in  water  and  in  alcohol,  but 
nearly  or  altogether  insoluble  in  ether.  When  their  aqueous  solu- 
tions are  treated  with  a  mineral  alkali,  the  alkaloid  is  liberated  and 
emits  its  peculiar  odor;  from  somewhat  strong  solutions  of  its  salts 
the  alkaloid  separates  in  the  form  of  minute  drops,  which  finally  col- 
lect upon  the  surface  of  the  mixture  as  an  oily  layer.  On  distilling 
an  aqueous  mixture  of  a  salt  of  conine  and  potassium  or  sodium 
hydrate,  the  liberated  alkaloid  passes  over  with  the  distillate.  If 
the  distillate  be  neutralized  with  oxalic  acid,  evaporated  to  dryness, 
and  the  residue  digested  with  alcohol,  the  oxalate  of  conine  will 
dissolve,  while  any  ammonium  oxalate  present  will  remain,  it  being 
insoluble  in  this  menstruum. 

In  the  examination  of  the  following  tests  for  conine  when  in  solu- 
tion, the  pure  alkaloid  was  dissolved  in  distilled  water.  When  a 
solution  of  this  kind  is  agitated,  it  forms  a  very  frothy  liquid,  even 
when  the  mixture  contains  only  the  l-10,000th  of  its  weight  of  the 
alkaloid.  The  fractions  indicate  the  fractional  part  of  a  grain  of  the 
alkaloid  in  solution  in  one  grain  of  water.  Unless'otherwise  stated, 
the  results  refer  to  the  reactions  of  one  grain  of  the  solution. 

1.  Auric  Chloride. 

A  saturated  aqueous  solution  of  conine  yields  with  excess  of 
trichloride  of  gold  a  copious,  bright  yellow,  amorphous  precipitate, 
which  is  insoluble  in  acetic  acid  and  in  diluted  hydrochloric  acid; 
with  a  less  quantity  of  reagent  the  precipitate  has  a  brownish  or 
reddish-brown  color.  When  treated  with  potassium  hydrate,  the 
precipitate  assumes  a  dark  color  and  finally  becomes  nearly  black. 

1.  -Y^  grain  of  conine,  in  one  grain  of  water,  yields  a  quite  copious 

precipitate. 

2.  -j^  grain  :  a  quite  good,  yellow  deposit, 

3.  j-Q^inr  grain :  an  immediate  cloudiness,  and  soon  a  very  satisfactory 

yellow  precipitate. 

4.  y^Viy  gi*!ii"  gives  but  little  indication  of  the  presence  of  the  alka- 

loid, even  after  the  mixture  has  stood  for  some  time. 
There  was  a  failure  to  obtain  crystals  from  any  of  the  foregoing 
mixtures. 


460  CONINE. 

2.  Picric  Add. 

Strong  aqueous  solutions  of  conine  yield  with  an  alcoholic  solu- 
tion of  picric  acid  a  yellow  amorphous  precipitate,  which  in  a  little 
time  changes  into  microscopic  globules,  and  these  after  a  time  deposit 
large,  yellow  crystals.  The  precipitate  is  insoluble  in  excess  of  the 
reagent,  but  readily  soluble  in  excess  of  the  alkaloid,  and  also  in  acetic 
acid. 

1.  y^  grain  of  conine  yields  a  copious  precipitate,  which  soon  be- 

comes crystalline,  Plate  VI.,  fig.  5.  If  the  mixture  be  stirred 
with  a  glass  rod,  it  immediately  yields  streaks  of  granules  and 
small  crystals. 

2.  -g^  grain  :  an  immediate  cloudiness,  and  in  a  little  time  a  quite 

good,  yellow,  amorphous  deposit. 

3.  Y^To    g^siii  yields  but   little  indication   of  the   presence   of  the 

alkaloid. 

3.  Mercuric  Chloride. 

This  reagent  produces  in  aqueous  solutions  of  conine  a  white, 
curdy  precipitate,  which  is  but  sparingly  soluble  in  water,  but  readily 
soluble  in  acetic  and  the  mineral  acids. 

1.  y^-Q   grain  of  conine  yields  a  copious,  white  precipitate,  which 

does  not  change  in  color,  and  remains  amorphous. 

2.  -g-^  grain  yields  an  immediate  turbidity,  and  soon  a  good  deposit. 

3.  YFoT  gi'ain  yields  in  a  few  moments  a  distinct  cloudiness,  and  in  a 

little  time  the  mixture  becomes  quite  turbid. 

4.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  an  aqueous  solution  of  potassium  iodide 
produces  in  solutions  of  conine  an  immediate  reddish-brown,  amor- 
phous precipitate,  which  soon  turns  yellow,  then  dissolves  to  a  clear 
solution ;  upon  further  addition  of  the  reagent,  the  precipitate  may 
be  reproduced,  even  several  times,  from  somewhat  strong  solutions 
of  the  alkaloid.  If  a  very  large  excess  of  the  reagent  be  at  first 
added,  the  precipitate  is  permanent.  It  is  readily  soluble  in  acetic 
acid. 

1.  Y^  grain  of  conine  yields  a  very  copious  precipitate. 

2.  yTqq  gi'^in '•  a  copious  deposit. 

3.  xo-.VoT  gi'aiii :  a  very  good,  brownish-yellow  precipitate. 


BROMINE    IN    UROMOIIYDRIC    ACID    TEST.  4G1 

4.  Tj^.^-^  i;raiii :  a  very  satisfactory,  yellowisli  deposit. 

5.  3Tj-,^Tnr  {?i'i^'"  yieltJ«  ii  quite  ^ood,  yellowisli  turbidity. 

6.  "nnj-^nro  J?i''i''^  '■  -^  distinct  turbidity, 

5.  Bromine  in  liromohydric  Acid. 

If  a  small  drop  of  anhydrous  conine  be  plaeed  in  a  watcli-<rlass, 
and  this  covered  by  an  inverted  glass  containing  a  drop  of  an  aqueous 
solution  of  bromohydric  acid  saturated  with  bromine,  the  glasses  be- 
come filled  with  dense,  white  fumes,  and  soon  crystalline  needles  form 
in  the  conine  drop,  and  this  on  spontaneous  evaporation  of  the  liquid 
leaves  a  mass  of  long,  colorless  needles ;  the  drop  of  reagent  also  leaves 
on  spontaneous  evaporation  a  very  good  deposit  of  similar  crystals. 
When  an  aqueous  solution  of  the  alkaloid  is  exposed  to  the  vapor 
of  the  reagent,  it  also  evolves  white  fumes,  even  when  the  solution 
contains  only  the  1-lOOOth  of  its  weight  of  conine. 

On  treating  anhydrous  conine  directly  with  the  above  reagent, 
it  yields  a  yellow,  amorphous  mass,  which  soon  becomes  converted 
into  large,  orange-colored  globules;  these  soon  become  yellow,  and 
after  a  time  deposit  colorless,  prismatic  crystals.  If  the  mixture  be 
evaporated  spontaneously,  it  leaves  a  mass  of  large  crystalline  needles, 
which  are  readily  soluble  in  alcohol,  and  reproduced  as  this  liquid 
evaporates.  These  reactions,  however,  are  modified  somewhat  by 
the  relative  quantities  of  conine  and  the  reagent  present. 

When  the  reagent  is  added  to  an  aqueous  solution  of  the  alka- 
loid, it  produces  a  yellow,  amorphous  precipitate,  which  after  a  time 
changes  into  oil-like  globules ;  upon  further  addition  of  the  reagent, 
the  yellow  amorphous  precipitate  is  reproduced.  On  allowing  the 
mixture  to  evaporate  spontaneously,  it  sometimes  leaves  a  crystalline 
residue,  but  sometimes  only  a  gummy  mass,  the  result  depending 
upon  the  relative  quantity  of  reagent  present.  The  precipitate  is 
readily  soluble  in  acids,  even  in  acetic  acid. 

1.  YWJ^  grain  of  conine,  in  one  grain  of  water,  when  exposed  to  the 
vapor  of  the  reagent,  yields  after  a  time  a  deposit  of  crystal- 
line needles ;  if  this  mixture  be  allowed  to  evaporate,  it  leaves 
a  mass  of  similar  crystals.  When  the  conine  solution  is  treated 
directly  with  the  reagent,  it  yields  a  copious,  yellow  precipitate, 
which  soon  becomes  converted  into  oily  globules.  If  large 
excess  of  the  reagent  has  been  avoided,  the  mixture  on  spon- 
taneous evaporation  leaves  a  mass  of  crystals. 


462  CONINE. 

2.  YWoT  gi'ain   yields  with  the  reagent  a  copious,   yellow  deposit, 

which  soon  dissolves,  but  is  reproduced  upon  further  addition 
of  the  reagent. 

3.  -3-^00"  E^^^^  '  a  good,  yellowish  deposit. 

4.  yo".VoT  gi^ain  yields  a  very  distinct  precipitate,  which  soon  dis- 

solves, and  is  not  reproduced   upon   further  addition  of  the 
reagent. 

6.  Silver  Nitrate. 

When  an  aqueous  solution  of  conine  is  treated  with  a  solution  of 
silver  nitrate,  it  yields  a  brownish  precipitate  of  silver  monoxide, 
which  soon  becomes  converted  into  the  suboxide  of  the  metal,  having 
a  nearly  black  color. 

1.  YUT  gi^ai"  of  conine  yields  a  quite  good  deposit. 

2.  YoVo  grain  :  an  immediate  precipitate,  and  in  a  little  time  a  good, 

flocculent  deposit. 

3.  3-0V0  grain :  a  slight  cloudiness,  and  in  a  little  time  a  quite  fair 

deposit. 

4.  xo.VoT  gi"ain :  after  some  minutes  the  mixture  presents  a  slight 

cloudiness. 

7.  Tannic  Acid. 

This  reagent  produces  in  aqueous  solutions  of  conine  a  white, 
amorphous  precipitate,  which  is  readily  soluble  in  a  small  quantity 
of  hydrochloric  acid,  but  is  reproduced  upon  further  addition  of  the 
acid,  and  then  is  insoluble  in  large  excess.  The  precipitate  is  per- 
manently soluble  in  acetic  and  nitric  acids,  as  also  in  excess  of  the 
conine  solution. 

1.  YTU  g^^ain  of  conine  yields  a  copious  precipitate. 

2.  y-joT  g^^ain  :  a  quite  good  precipitate. 

3.  Yo".Voo"  gi^ain  :  the  mixture  becomes  slightly  turbid. 

Other  Reagents. — As  conine  has  strong  basic  properties,  it  ore- 
cipitates  the  oxides  of  several  of  the  metals  from  solutions  of  their 
salts.  Mercurous  nitrate  produces  in  strong  aqueous  solutions  of  the 
alkaloid  a  dirty-brown  precipitate,  which  soon  becomes  nearly  black. 
One  grain  of  a  1-1 00th  solution  of  the  alkaloid  yields  a  very  copious 
deposit;  the  same  quantity  of  a  1-lOOOth  solution  yields  a  good, 
yellowish-white  precipitate;  and  a  l-5000th  solution,  a  dirty-white 
precipitate.     Lead   acetate   produces  in  a  1-1 00th  solution  of  the 


FALLACIES   OF   TFJ8T8.  463 

alkaloid  :i  (luitc  }j;o()(l,  white  deposit.     Copper  sulphate  gives  a  bluish 
precipitate,  which  is  insoluble  in  excess  of*  the  coiiine  solution. 

A  saturated  aqueous  solution  of  conine  yields  no  precipitate 
with  either  phitinic  chloride,  potassium  iodide,  potassium  chromate 
or  dichromate,  potassium  ferro-  or  ferricyanide,  or  ammonio  copper 
sulphate.  Should  the  alkaloid  contain  ammonia,  as  is  often  the 
case,  it  may  of  course,  when  treated  with  j)latinic  chloride,  yield  a 
yellow  precipitate  of  the  double  chloride  of  platinum  and  ammonium  ; 
but  the  correspond inji;  salt  of  conine  is  freely  soluble  in  water,  in 
which  respect  this  alkaloid  differs  from  ammonia,  and  also  from 
nicotine.  The  statement  of  Orfila,  that  lead  acetate  produces  no 
precipitate  with  conine,  is  true  only  of  somewhat  dilute  solutions  of 
the  alkaloid. 

Fallacies. — An  affirmative  reaction  of  none  of  the  above  tests 
for  conine  in  solution,  when  taken  alone,  is  characteristic  of  this 
alkaloid,  since  each  of  them  produces  similar  results  with  solutions 
of  various  other  substances.  But  by  the  concurrent  action  of  two 
or  more  of  these  tests,  especially  when  taken  in  connection  with  the 
odor  and  physical  state  of  conine,  the  presence  of  the  alkaloid,  even 
in  minute  quantity,  may  be  determined  with  certainty. 

Conine  and  nicotine  are  distinguished  from  other  alkaloids  in 
being  liquid  at  ordinary  temperatures,  by  their  peculiar  odor,  and  in 
that  Avhen  their  aqueous  solutions  or  solutions  of  their  salts  previously 
mixed  with  a  fixed  alkali  are  distilled,  they  appear  in  the  distillate 
and  impart  to  it,  at  least  after  concentration,  an  alkaline  reaction. 
In  this  connection,  however,  it  must  be  borne  in  mind  that  on 
distilling  a  mixture  containing  ammonia,  this  alkali  will  also  appear 
in  the  distillate  and  impart  to  it  an  alkaline  reaction;  but  this 
substance  is  readily  distinguished,  even  by  its  odor,  fi-om  the  volatile 
alkaloids. 

Conine  is  distinguished  from  nicotine:  1.  By  its  peculiar  odor, 
which  is  characteristic  even  in  highly  diluted  solutions;  2.  Its 
sparing  solubility  in  water  ;  3.  In  yielding  crystalline  needles  when 
exposed  to  the  vapor  of,  or  treated  directly  with,  hydrochloric  acid; 
4.  By  yielding  a  white  precipitate  with  corrosive  sublimate,  which 
remains  amorphous  and  unchanged  in  color ;  5.  Its  behavior  with 
picric  acid;  6.  Its  behavior  with  bromine  in  bromohydric  acid; 
7.  In  giving  a  dark  brown  precipitate  with  silver  nitrate;  and,  8. 


464  coxixE. 

By  failing  to  yield  a  precipitate  with  platinic  chloride.  On  com- 
paring the  special  reactions  of  these  alkaloids,  as  already  detailed, 
other  diiferences  will  be  observed. 

A  solution  of  couine  may  be  distinguished  from  ammonia  in  the 
same  manner  as  already  pointed  out  for  distinguishing  this  alkali 
from  nicotine,  in  the  special  reactions  of  the  latter. 

Sepaeatiox  FROii  Oegaxic  Mixtures. 

If,  in  poisoning  by  hemlock,  any  solid  parts  of  the  plant  are 
found,  they  may,  sometimes,  be  identified  by  their  botanical  char- 
acters (see  Pereira^s  Mat.  3Ied.,  ii.  727),  and  by  their  evolving  the 
peculiar  odor  of  conine  when  moistened  with  a  solution  of  potassium 
hvdrate  and  bruised  in  a  mortar. 

Conine  mav  be  recovered  from  organic  solutions,  the  contents  of 
the  stomach,  the  tissues,  and  the  blood,  in  precisely  the  same  manner 
as  alreadv  pointed  out  for  the  recovery  of  nicotine.  Since  most  of 
the  salts  of  conine  are  not  altogether  insoluble  in  ether,  if  this  liquid 
be  emploved  for  the  separation  of  foreign  organic  matter  from  an 
aqueous  solution  of  a  salt  of  this  kind,  the  decanted  ether  should  be 
reserved  for  future  examination,  if  necessary. 

A  fluid-ounce  of  blood  taken  from  each  of  the  two  cats  before 
referred  to — each  of  which  was  killed  by  a  single  drop  of  conine — 
was  examined  after  the  method  pursued  in  the  investigation  of  the 
blood  from  the  cats  poisoned  by  nicotine,  as  already  described.  The 
final  solution  from  the  blood  of  both  animals,  when  reduced  to 
three  drops  and  tested  by  its  odor  and  three  different  reagents,  gave 
results  which,  knowing  all  the  circumstances,  there  is  no  doubt  were 
due  to  the  presence  of  conine ;  yet  in  an  unknown  case  the  results 
would  by  no  means  have  justified  the  assertion  that  the  poison  was 
certainly  present.  On  mixing  the  1-lOOth  of  a  grain  of  conine 
with  an  ounce  of  normal  blood,  and  pursuing  the  above  method  of 
analvsis,  the  results  were  equivocal ;  but  when  the  l-25th  of  a  gra'n 
of  the  poison  was  added,  the  results  were  quite  satisfactory.  From 
a  comparison  of  the  special  tests  for  conine  and  nicotine,  it  is  quite 
obvious  that  they  will  indicate  with  certamty  the  presence  of  a  much 
smaller  quantity  of  the  latter  than  of  the  former  alkaloid. 

According  to  M.  Zalewski  {Virchow's  Jahresh.,  1869,  i.  365), 
conine  may  be  found  in  the  blood  after  ever\^  trace  has  disappeared 
from  the  stomach,  even  when  death  has  supervened  very  early;  and 


SEPARATION    FROM    ORGANIC    MIXTURES.  465 

the  poison  speedily  appears  in  tlio  uiino,  and  is  constantly  present  in 
this  excretion  durin<i;  the  course  of  the  toxic  symptoms.  According 
to  this  observer,  the  alkaloid  is  excreted  almost  entirely  throujrh  the 
kidneys,  and  it  was  detected  in  the  urine  of  a  dog  two  and  a  half 
tlays  after  the  administration  of  the  poison. 


80 


466  OPIUM. 


CHAPTEE   II 

OPIUM  AND   SOME   OF   ITS   CONSTITUENTS. 

I.  Opium. 

History  and  Chemical  Nature. — This  substance  is  the  concrete 
juice  of  the  Papaver  somniferum,  or  white  poppj,  and  is  obtained  by- 
making  incisions  into  the  capsules  when  in  their  unripe  state.  In 
regard  to  its  chemical  nature  opium  is  extremely  complex ;  and  its 
composition  varies  somewhat  in  the  several  commercial  varieties. 
Thus,  besides  gum,  resin,  coloring  matter,  and  inorganic  substances, 
it  contains,  according  to  the  results  of  different  observers,  some  fifteen 
or  more  crystallizable  organic  principles,  most  of  which  have  alka- 
loidal  properties.  Of  these  principles  the  only  ones  that  will  be 
separately  noticed  at  present  are  the  alkaloids  mor'phine,  narcotine, 
codeine,  and  narceine,  the  neutral  substance  opianyl,  or  meconin,  and 
the  organic  acid,  meconic. 

The  poisonous  properties  of  opium  are  due  chiefly  to  the  morphine 
which  it  contains,  which  is  present  principally  in  combination  with 
meconic  acid,  as  meconate  of  the  alkaloid.  Of  the  several  varieties 
of  opium,  the  Smyrna  is  usually  regarded  as  containing  the  greatest 
proportion  of  morphine.  From  the  best  samples  of  this  variety 
Merck  obtained  thirteen  per  cent,  or  more  of  the  alkaloid,  while 
from  the  poorest  he  obtained  only  from  three  to  four  per  cent.  On 
an  average,  perhaps,  opium  as  found  in  the  shops  contains  from  eight 
to  ten  per  cent,  of  morphine.  According  to  the  U.  S.  Pharmacopoeia, 
in  its  normal,  moist  condition  the  drug  should  contain  not  less  than 
nine  per  cent,  of  morphine.  Of  twenty  samples  of  opium  that  we 
examined,  the  average  proportion  of  morphine  was  9.85  per  cent.,  the 
extremes  being  8.41  and  11.29  per  cent,  of  the  alkaloid.  It  is  said 
that  certain  kinds  of  opium  sometimes  contain  twenty  per  cent.,  and 
even  more,  of  morphine. 


IMIYSH)r,<)(!I('AI-    EFFECTS.  467 

This  drug  is  sinnetimcs  tiiken  as  a  poison  in  its  solid  state,  but 
more  Irefpientlv  in  the  form  of  Laudanum,  or  Tincture  of  opium, 
wiiicii  is  an  aU-oholic  sohition  of  tlie  (huig.  Tiie  medicinal  dose  of 
opium  in  its  solid  form  for  an  adult  varies,  according  to  circumstances, 
from  half  a  grain  to  five  grains,  the  ordinary  dose  being  about  one 
ijrain  ;  the  dose  of  the  tincture,  under  like  circumstances,  varies  from 
ten  minims  to  one  fluid-drachm.  According  to  the  last  U.  S.  Phar- 
macopceia  (1880),  one  hundred  parts  by  weight  of  laudanum  should 
rej)resent  the  extractive  matter  of  ten  parts  of  dried  opium,  having 
a  morphine  strength  of  not  less  than  twelve  nor  more  than  sixteen 
per  cent.  About  eleven  minims,  or  twenty-two  drops,  would,  there- 
fore, represent  one  grain  of  opium ;  and  a  fluid-drachm  about  5.4 
grains  of  the  dried  drug.  Laudanum  yields  about  one  hundred  and 
twenty  drops  to  the  fluid-drachm. 

Since  opium  is  liable  to  considerable  variation  in  regard  to  the 
proportion  of  morphine  present,  and  as  the  strength  of  the  tincture 
is  much  influenced  by  the  strength  of  the  spirit  used  and  the  period 
of  maceration,  and,  also,  as  the  tincture  itself  is  sometimes  fraudu-. 
leutly  diluted,  it  is  obvious  that  laudanum,  as  found  in  the  shops,  is 
subject  to  great  variation  in  quality.  Of  forty-seven  samples  of 
laudanum  examined  by  H.  B.  Parsons,  of  New  York  {New  Remedies, 
July,  1883,  194),  the  amount  of  morphine  ranged  from  0.9  grain  to 
7.4  grains  per  fluid-ounce,  the  average  being  3.27  grains  ;  the  specific 
gravity  from  .938  to  .966  ;  and  the  weight  per  fluid-ounce  from  427.8 
to  440.5  grains.  These  samples,  however,  were  collected  from  dis- 
tant places  before  the  new  Pharmacopoeia  had  been  issued,  and  hence 
should  be  judged  by  the  standard  of  the  Pharmacopoeia  of  1870. 
Poisoning  l3y  opium  has  been  of  more  frequent  occurrence  than  per- 
haps by  any  other  known  substance. 

Symptoms. — When  a  poisonous  dose  of  opium  or  of  its  tincture 
has  been  swallowed,  the  patient  is  sooner  or  later  seized  with  confusion 
in  the  head,  giddiness,  and  stupor ;  the  stupor  soon  increases  in  inten- 
sity, and  eventuates  in  complete  insensibility.  In  this  state  the  res- 
piration becomes  slow;  the  pulse  full,  slow,  and  laboring;  the  eyes 
closed ;  the  pupils  usually  contracted  and  insensible  to  light,  and  the 
person  appears  as  if  in  a  profound  sleep.  As  the  case  advances,  the 
countenance  becomes  pale  and  ghastly;  the  lips  livid;  the  skin  cold 
and  moistened  with  perspiration  ;  the  breathing  slow  and  stertorous ; 
the   i)ulse  feeble  and  almost  imperceptible ;  the  limbs  relaxed,  and 


468  OPIUM. 

death  in  some  instances  is  preceded  by  convulsions.  Convulsions, 
however,  are  rarely  met  with  in  adults,  yet  they  are  not  uncommon 
in  children  :  when  they  do  occur  they  are  often  very  severe.  The 
pupils,  as  already  stated,  are  usually  contracted,  being  in  some  cases 
nearly  closed,  yet  they  are  not  unfrequently  dilated,  especially  in  the 
advanced  stage  of  the  case.  The  state  of  the  pulse  is  also  liable  to 
considerable  variation.  In  some  few  cases  vomiting,  and  in  other 
cases  purging,  has  occurred.  In  fact,  a  few  instances  are  related  in 
which  vomiting  was  about  the  only  symptom  produced  by  large  doses 
of  the  drug.  In  cases  of  recovery  from  large  doses  of  the  poison,  the 
stupor  is  often  followed  by  giddiness,  headache,  nausea,  and  vomiting. 

The  time  within  which  the  symptoms  first  manifest  themselves  is 
somewhat  various,  depending  upon  a  variety  of  circumstances,  but 
they  are  not  often  delayed  beyond  an  hour.  In  some  instances, 
especially  when  the  poison  is  taken  in  a  state  of  solution  and  on  an 
empty  stomach,  its  eifects  appear  within  a  few  minutes.  Dr.  Chris- 
tison  (op.  cit,  543)  refers  to  several  instances  in  which  the  symptoms 
occurred,  in  adults,  within  about  ten  minutes;  in  one  of  these,  the 
sopor  was  fairly  formed  in  fifteen  minutes  after  two  drachms  of  solid 
opium  had  been  taken.  In  a  case  quoted  by  Dr.  Taylor  {On  Poisons, 
588),  the  patient  was  totally  insensible  in  fifteen  minutes  after  the 
poison  had  been  swallowed. 

On  the  other  hand,  a  case  is  reported  in  which  a  woman  swal- 
lowed about  eight  ounces  of  solid  opium,  and  in  an  hour  afterward 
was  able  to  tell  connectedly  all  she  had  done  (see  post).  Another 
instance  is  related,  in  which  an  habitual  drunkard  took,  while  intoxi- 
cated, two  ounces  of  laudanum,  and  had  no  material  stupor  for  jive 
hours,  during  which  period  vomiting  could  not  be  induced.  Five 
hours  afterward  he  was  found  insensible,  and  he  eventually  died 
under  symptoms  of  opium  poisoning.  In  a  case  reported  by  Dr. 
G.  C.  Gibb,  a  healthy  man  swallowed,  with  suicidal  intent,  twelve 
drachms  of  laudanum,  and  no  symptoms  of  poisoning  manifested 
themselves  until  nine  hours  after  the  dose  had  been  taken;  spon- 
taneous vomiting  then  occurred,  and,  under  careful  treatment,  the 
patient  entirely  recovered.  {Amer.  Jour.  Med.  Sci.,  Jan.  1858, 
288.)  In  a  remarkable  instance  related  by  Dr.  Christison,  a  man 
swallowed  an  ounce  and  a  half  of  laudanum,  and  in  an  hour  after- 
ward half  as  much  more,  and  no  well-marked  symptoms  appeared 
until  the  eighteenth  hour.     The  patient  then  became  insensible,  and 


PERIOD   WHEN    FATAL.  469 

continued  in    this  condition   for  several   hours  ;    hut   he  eventually 
recovered. 

The  external  application  of  opium  to  an  ulcerated  or  abraded 
surface,  and  even  to  the  sound  skin,  has  in  several  instances  been 
followed  by  serious  results.  Thus,  a  child,  two  months  old,  nearly 
perished  in  consequence  of  a  cerate  containing  fifteen  drops  of  lauda- 
num having  been  kept  for  twenty-four  hours  on  a  slight  excoriation 
produced  by  a  fold  of  the  skin.  And  Sir  A.  Cooper  mentions  a 
c<ase  iu  which  a  solution  of  opium  applied  to  an  extensive  scald  on  a 
child  proved  fatal.  In  another  case,  a  young  man,  suffering  under 
some  slight  ailment,  applied  a  poultice  containing  a  large  quantity 
of  laudanum  to  the  sound  skin  over  the  pit  of  the  stomach,  after 
which  he  went  to  sleep.  Symptoms  of  narcotism  soon  appeared, 
and,  although  the  usual  treatment  was  employed,  the  patient  died 
from  the  effects  of  the  application.     (Stille's  Mat.  Med.,  i.  671.) 

The  administration  of  opium  in  the  form  of  enema  has  also  been 
followed  by  fatal  results.  In  a  case  quoted  by  Dr.  Beck,  twelve  drops 
of  laudanum,  used  as  an  injection  to  allay  the  pain  consequent  on 
cauterization  for  a  strictured  rectum,  produced  all  the  symptoms  of 
narcotic  poisoning,  and  death  in  seventeen  hours.  {Med.  Jur.,  ii. 
796.)  In  a  case  related  by  Dr.  J.  B.  Jackson, ^ye  drops  of  laudanum 
injected  into  the  rectum  of  a  child  eighteen  months  old  caused  death 
in  six  hours.  {Amer.  Jour.  Med.  ScL,  Oct.  1854,  384.)  In  this 
connection  it  may  be  mentioned  that  Dr.  Christison  states  that  he 
has  given  by  injection  one  fluid-draclim,  and  even  two  drachms,  of 
laudanum  without  producing  any  serious  symptoms. 

Period  when  Fatal.~The  ordinary  duration  of  fatal  poisoning  by 
opium,  according  to  the  observations  of  Dr.  Christison,  is  from  seven 
to  twelve  hours.  Several  instances,  however,  are  recorded  in  which 
death  took  place  with  much  more  than  the  usual  rapid itv.  In  a 
case  quoted  by  Dr.  Beck,  a  soldier  who  had  taken  two  ounces  and  a 
half  of  liquor  opii  sedativus  was  rendered  totally  insensible  in  fifteen 
minutes,  and  died  from  its  effects  in  one  hour  and  twenty  minutes. 
{Med.  Jur.,  ii.  792.)  Dr.  G.  Lyman  reports  a  case  in  which  an 
ounce  of  laudanum,  taken  by  a  woman,  aged  fifty-two  years,  pro- 
duced violent  symptoms  in  thirty-five  minutes,  and  death  in  three- 
quarters  of  an  hour.  {Amei\  Jour.  3Ied.  Sci.,  Oct.  1854,  383.) 
And,  in  the  Journal  just  cited,  a  case  is  reported  by  Dr.  Coale,  in 
which  death  took  place  within  the  same  brief  period.     These  are 


470  OPIUM. 

among  the  most  rapidly  fatal  cases  yet  recorded.  In  a  case  reported 
by  Dr.  J.  Dawson  [Ohio  Med.  and  Surg.  Journ.,  iii.  527),  about  an 
ounce  of  laudanum  proved  fatal  to  a  strong  man  in  six  hours. 

On  the  other  hand,  cases  are  related  in  which  death  was  delayed 
much  beyond  the  usual  period.  Thus,  several  instances  are  reported 
in  which  death  did  not  take  place  until  from  fifteen  to  twenty  hours 
after  the  poison  had  been  taken.  In  an  instance  related  by  Dr.  H. 
F.  Campbell,  in  which  nearly  three  ounces  of  laudanum  had  been 
swallowed  by  a  young  man,  aged  twenty-eight  years,  death  did  not 
ensue  until  after  twenty  hours.  {Amer.  Jour.  Med.  8ci.,  Oct.  1860, 
570.)  And  in  a  case  reported  by  M.  Alibert,  death  did  not  occur 
until  the  twenty-fourth  hour ;  and  in  another,  mentioned  by  Dr. 
Beck,  life  was  prolonged  until  the  forty-eighth  hour.  The  time 
within  which  death  takes  place  seems  to  have  but  little  relation  to 
the  quantity  of  poison  taken. 

Fatal  Quantity. — The  smallest  quantity  of  opium  that  may  destroy 
life  cannot  be  stated  with  certainty.  Dr.  Taylor  refers  to  an  in- 
stance in  which  ten  grains  of  the  solid  drug  proved  fatal  to  a  man ; 
and  another,  in  which  eight  grains  destroyed  the  life  of  a  woman. 
{On  Poisons,  598.)  And  Dr.  Christison  mentions  a  case  in  which 
four  grains  and  a  half,  mixed  with  nine  grains  of  camphor  taken  by 
an  adult,  was  followed  by  the  usual  symptoms  of  narcotism,  and 
death  in  nine  hours.  In  a  case  reported  by  Dr.  Morland  {Amer. 
Jour.  Med.  Sci.,  Oct.  1854),  five  grains  of  solid  opium,  taken  in  mis- 
take by  a  gentleman,  produced  all  the  usual  symptoms  of  the  drug, 
and  the  patient  barely  escaped  with  his  life.  In  another  case,  thirty- 
grains  of  the  drug  caused  death  in  eleven  hours. 

A  case  has  already  been  cited  in  which  an  ounce  of  laudanum 
proved  fatal  to  an  adult  in  three-quarters  of  an  hour.  And  in 
another  instance,  reported  by  Dr.  W.  F.  Norris  (Amer.  Jour.  Med. 
Sci.,  Oct.  1862,  397),  a  similar  quantity  caused  the  death  of  a  healthy 
man  in  about  eighteen  hours,  although  the  most  active  remedies  were 
employed.  In  a  case  for  the  details  of  which  I  am  indebted  to  Dr. 
R.  M.  Denig,  a  robust,  healthy  girl,  aged  seventeen  years,  in  a  fit  of 
despondency,  swallowed  two  drachms  by  measure  of  laudanum.  In 
about  three  hours  afterward  she  was  seized  with  stupor,  and  died 
under  the  usual  symptoms  of  narcotic  poisoning  in  about  seven  hours 
after  the  dose  had  been  taken.  The  respectable  druggist  who  pre- 
pared and  sold  her  the  laudanum  testified  that  at  most  it  contained 


FATAL   QUANTITY.  471 

tlu'  soluble  portion  of  only  seven  giains  of  opium.  Dr.  Too^^ood 
relates  an  instanec  in  which  twelve  drops  of  "  Battley's  sedative," — 
wiiieii  is  usually  regarded  as  having  about  three  times  the  strength  of 
ordinarv  laudanum, — talcon  by  a  feeble  woman,  aged  fifty-five  years, 
pnniuced  the  usual  synij)toms  of  opium  poisoning,  and  death  on  the 
following  day.     {Provincial  Med.  and  Surg.  Jovr.,  Nov.  1841,  129.) 

Numerous  instances  are  recorded  in  which  extremely  small  quan- 
tities of  opium  proved  fatal  to  very  young  children.  In  a  case  that 
fell  under  our  own  observation,  three  drops  of  laudanum  caused  the 
death  of  a  child  two  weeks  old  in  about  six  hours.  In  a  ca.se  men- 
tioned by  Dr.  Beck,  two  drops  of  laudanum,  given  four  times  during 
a  period  of  eighteen  hours,  proved  fatal  to  a  child  six  weeks  old. 
Even  a  single  dose  of  two  drops  of  laudanum  caused  the  death 
of  an  infant  four  days  old ;  and  in  another  instance,  an  infant  six 
davs  old  was  killed  by  a  single  drop  of  the  opiate  preparation.  Dr. 
Schaefer  reports  an  instance  in  which  three-quarters  of  a  grain  of 
solid  opium  taken  in  two  doses,  one-half  the  quantity  being  admin- 
istered five  hours,  and  tlie  remainder  three  hours,  before  death, 
proved  fatal  to  a  child.  In  a  recent  instance  [Med.  Times,  Jan.  1880, 
165),  about  two  and  a  half  grains  of  the  drug  caused  the  death  of 
a  child,  nineteen  months  old,  in  nine  and  a  half  hours. 

Notwithstanding  these  facts,  recovery  has  not  unfrequently  taken 
place  after  very  large  quantities  of  the  drug  had  been  taken.  In  a 
case  reported  by  Dr.  J.  B.  Jackson,  a  woman  swallowed  ninety  grains 
of  solid  opium,  and  was  not  seen  by  a  physician  until  three  hours 
after  the  occurrence.  She  was  then  laboring  under  all  the  symptoms 
of  opium  poisoning ;  yet,  under  active  treatment,  she  eventually  re- 
covered. {Amer.  Jour.  Med.  Sci.,  Oct.  1854,  385.)  In  another  case, 
a  stout,  muscular  woman,  who,  under  disguise,  had  served  several 
months  as  a  common  soldier  in  the  late  war,  took  for  the  purpose  of 
self-destruction  sixty  grains  of  solid  opium;  in  about  two  hours 
afterward,  being  disappointed  in  the  effects  of  the  drug,  she  swal- 
lowed half  an  ounce  of  laudanum,  and  about  half  an  hour  later 
took  as  much  more.  When  seen,  about  three  hours  and  a  half  after 
taking  the  first  dose,  by  Dr.  J.  B.  Thompson,  to  whom  I  am  indebted 
for  the  particulars  of  the  case,  she  was  perfectly  rational,  and  told  all 
she  had  done.  Emetics  of  sulphate  of  zinc  and  ipecacuanha  were 
then  administered,  but  they  did  not  operate  until  after  about  half  an 
hour,  when  they  brought  away  a  large  mass  of  matter  having  a  strong 


472  OPIUM, 

opiate  odor ;  the  vomiting  was  kept  up  for  about  three-quarters  of 
an  hour.  She  at  no  time  suffered  severe  narcotism,  was  soon  out  of 
danger,  and  rapidly  recovered.  From  several  circumstances  connected 
with  this  case,  there  is  no  doubt  that  the  patient  took  the  quantities 
of  opium  and  laudanum  stated,  which  are  equal  to  nearly  one  hundred 
grains  of  the  crude  drug. 

One  of  the  most  remarkable  cases  of  this  kind  yet  recorded  is 
the  following.  A  pregnant  woman,  aged  thirty-two  years,  took, 
with  suicidal  intent,  between  seven  and  eight  ounces  of  solid  opium. 
When  seen  by  a  physician  in  about  an  hour  afterward,  she  was  able 
to  relate  in  a  connected  manner  the  history  of  her  case.  The  admin- 
istration of  an  emetic  caused  copious  vomiting,  by  which  lumps  of 
opium  of  the  size  of  hazelnuts  were  ejected.  The  emetic  was  re- 
peated, and  its  operation  encouraged  by  large  draughts  of  warm 
water:  it  was  presumed  that  this  vomiting  brought  away  at  least 
three  ounces  more  of  opium.  The  patient  then  fell  into  a  deep  sleep, 
from  which  she  could  with  difficulty  be  roused ;  but  at  length  she 
became  more  sensible,  and  complained  of  violent  burning  pain  in 
the  stomach.  After  a  little  time  a  reaction  took  place,  and  symp- 
toms of  phrenitis  manifested  themselves ;  but  she  finally  recovered. 
[American  Medical  Recorder,  xiii.  418.) 

Treatment. — In  poisoning  by  opium  or  any  of  its  prepara- 
tions, any  portion  of  the  unabsorbed  poison  should  be  quickly  re- 
moved from  the  stomach.  For  this  purpose  the  stomach-pump  will 
usually  be  found  the  most  efficient;  but  in  the  absence  of  this  instru- 
ment an  emetic  of  from  twenty  to  thirty  grains  of  sulphate  of  zinc 
or  about  ten  grains  of  sulphate  of  copper  should  be  exhibited.  If 
neither  of  these  emetics  be  at  hand,  powdered  mustard  or  a  solution 
of  common  salt  should  be  freely  administered.  If  symptoms  of 
narcotism  have  already  manifested  themselves,  an  emetic  may  fail  to 
act.  Under  these  circumstances,  therefore,  great  caution  should  be 
exercised  in  the  administration  of  any  of  the  more  poisonous  emetics, 
such  as  the  sulphate  of  copper  and  tartar  emetic. 

For  the  purpose  of  producing  emesis  in  cases  of  this  kind. 
Dr.  A.  liouth  advises  [London  Lancet,  April,  1883,  316)  a  two  per 
cent,  solution  of  apomorphia,  administered  subcutaneously  in  doses 
of  from  three' to  ten  minims.  This  will  usually  cause  emesis  in  from 
two  to  five  minutes,  the  contents  of  the  stomach  being  generally 
voided  in  one  rush  without  previous  nausea. 


ANTIDOTES.  473 

During  the  progress  of  the  case  it  is  of  the  utmost  importance 
that  the  patient  be  kept  constantly  roused.  For  this  purpose  various 
methods  have  been  advised,  such  as  keeping  the  patient  in  continual 
motion,  flagelhxtions  with  wet  cloths,  and  the  dashing  of  cold  water 
over  the  head  and  chest.  Sometimes  the  dashing  of  cold  water  over 
the  patient  insures  the  operation  of  an  emetic.  One  of  the  most 
efficient  methods  yet  proposed  for  preventing  a  state  of  insensibility 
or  for  rousing  the  individual  from  this  condition  is  a  current  of 
magneto-electricity  applied  to  the  spine  and  chest.  Many  cases  are 
reported  in  which  this  method  was  employed  with  complete  success ; 
and  we  have  in  two  instances  used  it  with  similar  results.  {Ohio  Med. 
and  Surg.  Jour.,  May,  1858,  388.)  As  a  stimulant,  a  strong  decoc- 
tion of  coffee  has  been  highly  recommended  ;  in  fact,  several  instances 
are  reported  in  which  it  is  claimed  that  a  decoction  of  this  kind  was 
the  means  of  saving  life.  In  extreme  cases  artificial  respiration  has 
been  employed  with  great  advantage. 

As  a  chemical  antidote,  Orfila  advised  the  free  administration  of 
vegetable  solutions  containing  tannic  acid,  on  the  ground  that  this 
acid  forms  with  the  active  principle  of  opium  a  compound  only 
sparingly  soluble  in  water.  So,  also,  solutions  of  iodine  and  of 
bromine  have  been  strongly  recommended.  In  practice,  however, 
these  substances  have  been  found  of  little  service.  Various  other 
chemical  antidotes  have  been  proposed  ;  but  the  utility  of  these 
seems  to  be  even  more  doubtful  than  that  of  the  substances  already 
mentioned. 

From  the  antagonistic  action,  whether  apparent  or  real,  existing 
between  the  physiological  effects  of  opium  and  those  of  belladonna 
(or  its  active  principle  atropine),  it  was  long  since  claimed  that  these 
substances  are  mutually  antidotal  to  each  other;  and  within  late 
years  numerous  instances  have  been  reported  which  seem  to  leave 
no  doubt  whatever  as  to  the  reciprocal  antidotal  action  of  these 
substances. 

A  case  of  this  kind,  in  which  it  is  believed  that  three  ounces  of 
laudanum  had  been  taken,  is  related  by  Dr.  H.  J.  Horton.  {Med. 
and  Surg.  Reporter,  Philadelphia,  Sept.  1866,  225.)  Out  of  nine 
cases  of  opium  poisoning  treated  by  belladonna,  and  eighteen  of  bella- 
donna poisoning  treated  by  opium,  collected  by  Dr.  AV.  Xorris,  of 
Philadelphia,  only  two  of  the  former  and  one  of  the  latter  proved 
fatal.     {Amer.  Jour.  Med.  Sci.,  Oct.  1862,  395.)      Of  eleven  cases 


474  opnj:\r. 

of  opium  poisoning  treated  by  the  hypodermic  injection  of  atropine, 
by  D.  J.  Johnston,  of  Shanghai,  all  the  patients  recovered.  (Jled.- 
Chir.  Rev.,  Jan.  1873,  248.) 

PosT-MOETEii  Appeaeaxces. — The  most  common  morbid  ap- 
pearances after  death  from  poisoning  by  this  substance  are  turges- 
cence  of  the  blood-vessels  of  the  brain,  effusion  between  the  mem- 
branes and  into  the  ventricles  of  this  organ,  a  congested  state  of  the 
hmgs,  and  general  fluidity  of  the  blood.  But  these  appearances  are 
by  no  means  constant,  nor  are  they  peculiar  to  death  from  opium. 
In  some  few  instances  the  mucous  membrane  of  the  stomach  has  pre- 
sented a  reddened  appearance  ;  but  not,  perhaps,  as  the  direct  result 
of  the  action  of  the  poison,  ^hen  the  poison  has  been  taken  in  its 
crude  state  or  in  the  form  of  laudanum,  the  contents  of  the  stomach 
not  unfrequently  evolve  the  peculiar  odor  of  opium ;  but  even  this 
character  is  often  wanting,  the  poison  having  disappeared  from  the 
stomach  prior  to  death. 

In  a  case  related  by  Dr.  C.  A.  Lee,  in  which  a  large  quantity  of 
laudanum  had  been  taken  and  death  did  not  occur  until  the  sixteenth 
hour,  the  superficial  veins  of  the  scalp  were  found  very  full  of  dark, 
uncoagulated  blood.  The  longitudinal  and  lateral  sinuses  of  the 
brain  were  distended  with  blood;  and  between  the  pia  mater  and 
arachnoid  membrane  there  was  a  large  collection  of  serum,  of  a 
yellowish  hue.  The  choroid  plexus  was  very  vascular,  and  in  the 
bottom  of  the  ventricles  there  were  small  flakes  of  purulent  matter. 
The  lungs  were  congested ;  and  the  right  side  of  the  heart  was  full 
of  coagulated  blood.  The  mucous  villi  of  the  cardiac  orifice  of  the 
stomach  were  redder  than  natural  and  much  softened.  The  termina- 
tion of  the  oesophagus  seemed  inflamed,  and  the  mucous  lining  of  the 
intestines  erythematous.    (Neiv  York  Med.  and  Fhys.  Jour.,  xxx.  297.) 

In  Dr.  Dawson's  case,  in.  which  death  occurred  in  six  hours,  the 
bodv  and  limbs  presented  a  bluish  appearance,  and,  although  the 
inspection  was  made  while  the  body  was  still  warm,  the  limbs  were 
stiff  and  unyielding.  The  membranes  of  the  brain  were  found 
congested,  and  the  arteries,  veins,  and  sinuses  were  filled  with  dark 
blood.  The  lungs  appeared  natural ;  when  cut,  dark  blood  flowed 
freely  from  the  vessels.  The  liver  was  healthy.  The  mucous  mem- 
brane of  the  stomach  around  the  cardiac  and  pyloric  orifices  was  in 
a  state  of  hyperseniia,  being  most  intense  and  extensive  about  the 
former. 


PHYSICAL    AND   CHEMICAL    PROPERTIES.  475 

In  a  case  reported  by  Dr.  Ogle  {St.  Gewge's  Hosp.  Rep.,  1868, 
224),  the  contents  of  tlie  cranium  were  natural,  there  being  no  ex- 
tensive congestion  or  effusion  of  fluid  found  in  the  cavities  or  mem- 
branes. In  the  case  observed  by  Dr.  Schaefer,  there  was  a  spongy 
condition  of  the  lungs,  which  were  gorged  with  black,  fluid  blood  ; 
hypersemia  of  the  liver  and  spleen,  and  a  full  urinary  bladder.  The 
vessels  of  the  brain  were  filled  with  dark,  fluid  blood  ;  and  the  ven- 
tricles contained  a  large  quantity  of  effused  serum,  and  several 
drachms  of  a  similar  fluid  were  found  at  the  base  of  the  brain. 

Physical  and  Chemical  Properties. — Opium,  in  its  solid 
state,  has  a  reddish-brown  color,  a  well-marked  and  peculiar  odor, 
and  a  bitter,  acrid  taste.  The  odor  of  this  drug  readily  serves  to 
distinguish  it  from  all  other  substances  except  lactucarium,  which 
has  a  somewhat  similar  otlor.  When  fresh,  opium  is  quite  soft  and 
plastic,  but  on  exposure  to  the  air  it  slowly  becomes  hard  and  brit- 
tle, and  is  then  readily  reduced  to  a  yellowish-brown  powder.  When 
moderately  heated,  it  melts  to  a  serai-fluid  mass,  which  readily  takes 
fire,  burning  with  a  bright  flame.  It  is  somewhat  heavier  than 
water,  its  density  being  about  1.32.  Laudanum,  or  the  alcoholic 
solution  of  opium,  as  found  in  the  shops,  has  a  deep  brownish-red 
color,  and  the  odor  and  taste  of  the  solid  drug.  The  active  proper- 
ties of  opium  are  also  taken  up  by  water,  when  the  drug  is  digested 
in  this  liquid  ;  this  extraction  is  much  facilitated  by  a  moderate  heat, 
and  also  by  the  presence  of  a  free  acid.  Chloroform  and  ether,  in 
their  pure  state,  fail  to  withdraw  the  active  principles  of  the  drug. 

Since,  as  already  pointed  out,  opium  consists  of  a  number  of 
different  substances,  it  is  obvious  that  there  can  be  no  single  chemi- 
cal reagent  that  will  show  its  presence  as  a  whole ;  but  this  may  be 
inferred  by  proving  the  presence  of  one  or  more  of  the  substances 
peculiar  to  it.  Although  opium  contains  several  such  substances, 
the  ones  usually  sought  for,  in  medico-legal  investigations,  are  mor- 
phine and  meconic  acid.  Since  morphine,  as  well  as  several  of  its 
salts,  is  frequently  administered  or  taken  alone,  it  is  obvious  that 
proof  of  the  presence  of  this  alkaloid  alone  would  not  in  all  cases 
justify  the  inference  that  opium  was  present.  This  deficiency,  how- 
ever, is  always  supplied  when  the  presence  of  meconic  acid  has  been 
established. 

Before  considering  the  methods  by  which  morphine  and  meconic 


476  MORPHINE. 

acid  may  be  separated  from  complex  organic  mixtures  of  the  crude 
drug,  the  special  properties  of  these  substances  will  be  described. 
The  chemical  properties  of  some  of  the  other  principles  peculiar  to 
opium  will  then  be  considered. 

II.  Morphine. 

History  and  preparation. — Morphine,  as  found  in  nature,  occurs 
only  in  opium,  in  which  it  exists  chiefly  in  combination  with  rae- 
conic  acid,  but  partly  with  sulphuric  acid.  This  alkaloid  was  discov- 
ered, in  1804,  by  Sertiirner ;  its  composition,  according  to  Laurent, 
is  Ci7Hi9lS[03,H20 ;  molecular  weight  303. 

Morphine  may  be  obtained,  according  to  the  method  of  Gregory, 
by  treating  a  concentrated  aqueous  solution  of  opium  with  slight 
excess  of  a  solution  of  calcium  chloride.  After  a  little  time,  es- 
pecially if  warmed,  the  mixture  deposits  a  copious  precipitate,  con- 
sisting of  a  mixture  of  meconate  and  calcium  sulphate,  while  hydro- 
chloride of  morphine  remains  in  solution.  The  liquid  is  then  filtered, 
and  the  highly  colored  filtrate  concentrated  to  the  consistency  of  a 
thin  syrup,  when,  on  cooling,  the  hydrochloride  of  morphine  sepa- 
rates in  its  crystalline  state,  forming  a  nearly  solid  mass.  This  is 
strongly  pressed  in  muslin,  redissolved  in  a  small  quantity  of  hot 
water,  the  solution  filtered,  and  the  salt  allowed  to  recrystallize ;  this 
operation  is  repeated  a  second  and,  if  necessary,  a  third  time,  using 
a  little  prepared  animal  charcoal  to  absorb  the  coloring  matter.  The 
salt  is  now  dissolved  in  hot  water,  and  the  solution  slightly  super- 
saturated with  ammonia,  when,  on  standing,  the  liberated  alkaloid 
is  deposited  in  snow-white  crystals. 

Various  methods  have  been  proposed  for  the  quantitative  deter- 
mination of  the  morphine  present  in  crude  opium.  Of  several  of 
these  that  we  have  examined,  that  advised  by  E.  F.  Teschemacher 
[Chem.  News,  Feb.  1877,  47),  although  somewhat  tedious,  gave  the 
most  satisfactory  results,  especially  in  regard  to  freedom  from  color 
and  the  purity  of  the  final  product. 

Symptoms. — Considerable  difference  of  opinion  has  existed  as  to 
whether  or  not  the  eifects  of  morphine  and  its  salts  were  identical 
with  those  occasioned  by  opium;  but,  on  the  whole,  the  syraj)toms 
are  much  the  same,  only  that  the  effects  of  the  saline  combinations 
of  the  alkaloid  usually  manifest  themselves  more  promptly  than  in 


PHYSIOLOGICAL   EFFECTS.  477 

the  case  of  the  •rude  drug.  In  addition  to  the  usual  narcotic  symp- 
toms, itchiii*;  of  the  skin,  impaired  or  total  loss  of  vision,  and  in- 
ability to  void  urine,  have  frequently  been  observed.  Great  lividity 
of  the  skin  has  also  frequently  been  present.  The  relative  strength 
of  morphine  and  its  salts  is  generally  estimated  to  be  about  five  or 
six  times  that  of  the  crude  drug. 

In  a  ease  reported  by  Dr.  Houston,  ten  grains  of  the  sulphate  of 
morphine,  given  by  mistake  to  a  gentleman,  aged  fifty-nine  years, 
who  was  laboring  under  intermittent  fever,  caused  death  in  less  than 
two  hours,  although  various  remedies  were  employed.-  Deep  ster- 
torous breathing  was  the  only  symptom  observed.  {Beck's  Med. 
Jur.,  ii.  799.)  Dr.  Christison  mentions  an  instance  in  which  a  girl, 
who  had  taken  ten  grains  of  the  hydrochloride,  was  seized  with 
narcotic  symptoms  within  fifteen  minutes  afterward,  and  died  from 
its  effects  in  twelve  hours.  {Op.  ciL,  558.)  In  a  case  reported  by 
Prof.  C.  Shepard  {Pamphlet,  1879),  seven  and  a  half  grains  of  the 
sulphate  caused  the  death  of  a  man  in  less  than  two  hours.  Dr. 
Ebertz  relates  a  case  in  which  something  less  than  four  grains  of  the 
hydrochloride,  taken  by  a  woman  in  mistake  for  quinine,  proved 
fatal  in  fifty  minutes.  {Ann.  (VHyg.,  July,  1875,  220.)  And  in  a 
case  reported  by  Dr.  D.  W.  Prentiss  {Amer.  Jour. -Med.  ScL,  April, 
1867,  562),  two  pills,  containing  about  three  grains  of  the  alkaloid, 
caused  the  death  of  a  young  mulatto,  aged  sixteen,  in  twelve  hours. 

In  a  case  quoted  by  Wharton  and  Stille  {3Ied.  Jur.,  581),  a  gen- 
tleman affected  with  acute  rheumatism  died  from  the  effects  of  one 
grain  and  a  third  of  morphine,  taken  in  four  pills  at  intervals  of  an 
hour  between  each.  One  grain  of  the  acetate  administered  by  mis- 
take to  a  debilitated  woman  caused  her  death  in  about  eleven  hours. 
And  in  another  instance,  one  grain  of  the  hydrochloride,  taken  in 
divided  doses  over  a  period  of  six  hours,  proved  fatal  to  a  girl  nine- 
teen years  old.  In  a  case  reported  by  Dr.  Toogood,  seven  drops  of 
a  solution  of  the  acetate  of  morphine  (strength  not  stated)  destroyed 
the  life  of  an  aged  woman,  under  the  usual  narcotic  symptoms,  in 
about  twelve  hours.  {Provincial  Med.  and  Surg.  Jour.,  Nov.  1841, 
129.)  A  solution  containing  only  the  twelfth  part  of  a  grain  of 
morphine,  administered  by  mistake,  caused  the  death  of  an  infant. 
{Chemical  News,  London,  Aug.  1863,  98.) 

On  the  other  hand,  Mr.  Winterbotham  reports  a  case  in  which  a 
child,  two  years  and  three  months  old,  swallowed  one  grain  of  the 


478  MORPHINE. 

acetate  of  morphine  in  solution,  and  the  poison  remained  undisturbed 
in  the  system  for  two  hours  and  a  half.  At  the  end  of  this  period, 
free  vomiting  was  induced  by  an  emetic  of  sulphate  of  zinc ;  and 
under  the  use  of  the  ordinary  remedies  the  child  entirely  recovered. 
{Amer.  Jour.  Med.  Sci.,  April,  1863,  520.)  In  a  case  related  by 
Orfila,  a  young  man  entirely  recovered  within  three  days,  after 
having  taken,  with  suicidal  intent,  twenty  grains  of  the  hydrochlo- 
ride of  morphine.  Within  ten  minutes  after  taking  the  poison,  the 
patient  experienced  a  sense  of  heat  in  the  stomach,  with  intense 
itching  of  the  skin ;  but  over  four  hours  elapsed  before  symp- 
toms of  stupor  manifested  themselves.  Profound  insensibility  then 
supervened,  and  he  was  affected  with  trismus;  the  pupils  became 
slightly  dilated  ;  the  surface  of  the  body  cold ;  the  pulse  rapid ; 
the  breathing  hurried  and  stertorous ;  the  abdomen  tense  and 
tympanitic,  and  there  were  occasional  convulsions  ;  and  afterward 
he  had  difficult  and  scanty  micturition,  with  pain  in  the  kidneys 
and  bladder,  and  difficulty  of  swallowing. 

A  somewhat  similar  case  to  that  just  mentioned  is  cited  by  Dr. 
Christison,  in  which  a  young  man  swallowed  fifty  grains  of  the  ace- 
tate of  morphine,  and  although  he  was  seized  within  fifteen  minutes 
with  the  usual  narcotic  symptoms  of  the  poison  in  an  aggravated 
degree,  and  vomiting  could  not  be  induced  until  four  hours  after- 
ward, he  finally  recovered.  In  a  case  reported  by  Dr.  Wood  {Boston 
Med.  and  Surg.  Jour.,  July,  1876,  82),  about  sixty  grains  of  the 
acetate  had  been  taken,  and  the  patient  finally  recovered,  although 
no  treatment  was  employed  until  four  hours  after  the  poison  had 
been  taken. 

One  of  the  most  remarkable  cases  of  recovery  yet  reported  is  the 
following,  related  by  Dr.  W.  F.  Norris  {Amer.  Jour.  Med.  Sol.,  Oct. 
1862,  395).  A  druggist,  aged  nineteen  years,  for  the  purpose  of 
self-destruction,  swallowed  seventy-five  grains  of  the  sulphate  of  mor- 
phine. No  marked  symptoms  appeared  for  an  hour  and  a  half  after- 
ward, when  he  began  to  feel  sleepy  and  had  a  staggering  gait.  Soon 
after  this  emetics  were  given,  with  the  effect  of  producing  free  emesis. 
The  patient  then  became  unconscious,  the  pupils  contracted  to  the 
size  of  a  pin's  point,  the  pulse  soft  and  frequent,  and  the  respiration 
slow  and  labored :  but  under  the  active  use  of  remedies,  including 
extract  of  belladonna,  the  cold  douche,  and  galvanism,  he  was  quite 
well  on  the  second  day  after  the  occurrence. 


PHYSIOLOGICAL    EFFECTS.  170 

A  case  is  reportetl  by  Dr.  Du  Bois  [Western  Lancet,  June,  1872) 
in  which  recovery  took  place,  under  active  treatment,  inchidiiij^  large 
dosi's  of  belladonna,  after  eighti/  grains  of  the  sulphate  of  moi'phine 
had  bet'n  taken  in  two  doses;  and  Dr.  Chisolni  relates  anf)ther 
(Maryland  Med.  Jour.,  June,  1878),  in  which  one  hundred  and 
twenty  grains  of  the  salt  had  been  taken  at  a  single  dose,  and  the 
patient  recovered. 

The  external  applicaiion  of  morphine  to  abraded  surfaces,  as  well 
as  its  use  in  the  form  of  enema,  has  in  several  instances  been  fol- 
lowed by  serious  and  even  fatal  results.  A  quantity  of  the  alkaloid, 
perhaps  about  one  grain,  applied  to  a  blistered  surface  on  the  back 
of  the  neck  of  an  aged  lady,  produced,  in  the  course  of  about  two 
hours,  convulsive  agitations,  cold  sweats,  extreme  prostration,  and 
threatened  suffocation,  from  which  the  patient,  under  active  treat- 
ment, only  slowly  recovered.  [American  Medical  Intelligencer,  ii.  13.) 
In  a  case  quoted  by  Dr.  A.  Stille  [3Iat.  Med.,  i.  676),  a  lady  affected 
with  cancer  of  the  uterus  was  dangerously  narcotized  by  less  than 
one-sixteenth  of  a  grain  of  hydrochloride  of  morphine  applied  to 
the  denuded  skin  of  the  epigastrium.  Even  the  one-thirty-second 
of  a  grain  of  the  alkaloid  applied  in  this  manner  has  produced  very 
serious  symptoms. 

An  enema  containing  ten  grains  of  sulphate  of  morphine,  pre- 
scribed in  mistake  for  quinine,  was  administered  to  a  child  five  years 
old,  who  was  laboring  under  intermittent  fever.  Within  ten  min- 
utes the  child  became  sleepy,  and  shortly  afterward  it  was  seized  with 
violent  convulsions  ;  various  remedies  were  now  employed,  but  death 
speedily  ensued.  [Med.-Chir.  Rev.,  xv.  551.)  In  another  instance, 
reported  by  Dr.  Anstie,  three  grains  of  the  alkaloid  given  inadver- 
tently as  an  injection  caused  death  in  about  sixteen  hours.  [Amer. 
Jour.  Med.  Sci.,  April,  1863,  520.)  The  age  of  the  patient  in  this 
case  is  not  stated ;  but  it  would  seem  that  the  person  was  an  adult. 

Administered  hypode)'micaUy ,  even  in  only  minute  quantity,  mor- 
phine has  in  several  instances  produced  very  unexpected  results. 
Thus,  an  instance  is  related  in  which  half  a  grain,  employed  in  this 
manner  for  the  relief  of  sciatica,  proved  fatal  to  a  woman,  aged  fifty 
years.  So,  also,  a  case  is  reported  in  Avhich  one-third  of  a  grain  pro- 
duced profound  stupor ;  and  another  [Boston  Med.  and  SxLrg.  Jour., 
Oct.  1879,  619),  in  which  about  one-eighth  of  a  grain  of  the  sulphate 
caused  most  singular  and  alarming  symptoms. 


480  MORPHINE. 

The  Treatment  in  poisoning  by  morphine  or  any  of  its  salts  is  the 
same  as  that  for  opium  poisoning,  already  considered. 

Post-mortem  Appearances. — These  are  the  same  in  kind  as 
found  in  poisoning  by  opium.  .  In  a  case  reported  by  Dr.  J.  Dawson 
[Ohio  Med.  and  Surg.  Jour.,  iii.  525),  in  which  a  young  woman, 
with  suicidal  intent,  took  about  fifty  grains  of  morphine,  and  died 
from  its  effects  in  forty-eight  hours,  seventeen  hours  after  death  the 
arteries,  veins,  and  sinuses  of  the  brain  were  found  engorged  with 
black,  fluid  blood ;  and  the  ventricles  contained  about  a  drachm  of 
colored  serum.  The  lungs  were  normal  in  appearance ;  the  ventricles 
of  the  heart  contained  black  blood,  the  right  being  the  fullest.  The 
mucous  membrane  of  the  stomach,  for  about  one-third  of  its  surface, 
was  hypersemic,  especially  about  the  cardiac  orifice. 

In  the  case  reported  by  Dr.  Prentiss,  already  cited,  there  was 
found  congestion  of  the  brain,  the  blood  was  quite  fluid,  and  a  fibrin- 
ous clot  was  found  in  the  longitudinal  sinus;  there  was  no  fluid  in 
the  ventricles  nor  in  the  cavity  of  the  arachnoid.  The  abdominal 
organs  were  all  normal  in  appearance.  The  cavity  of  the  thorax  was 
not  examined. 

Chemical  Properties. 

General  Chemical  Nature. — Morphine  in  its  pure  state  crys- 
tallizes in  the  form  of  short,  colorless,  odorless,  rectangular  prisms, 
which  contain  one  molecule  of  water  of  crystallization,  CiyH^gNOg, 
HgO.  The  exact  forms  of  these  crystals,  however,  are  subject  to 
considerable  variation,  depending  somewhat  upon  the  method  em- 
ployed for  their  preparation  and  the  strength  of  the  solution  from 
which  they  were  separated,  and  even  upon  the  quantity  of  the  solu- 
tion employed.  When  gently  heated,  the  crystals  part  with  their 
water  of  crystallization  and  become  opaque ;  at  a  little  higher 
temperature,  they  fuse  to  a  brownish  liquid,  which,  if  the  heat  be 
increased,  evolves  dense,  white  fumes,  then  turns  black,  and  is  finally 
consumed.  Morphine  has  a  very  bitter  taste  and  strong  basic  prop- 
erties. It  completely  neutralizes  diluted  acids,  forming, salts,  most 
of  which  are  crystallizable.  It  is  readily  decomposed  by  concen- 
trated nitric  acid  and  by  hot  sulphuric  acid ;  but  not  by  the  cold 
caustic  alkalies. 

Solubility.  1.  In  Water. — When  excess  of  pure,  powdered  mor- 
phine is  frequently  agitated  for  twelve  hours  with  water  at  the  ordi- 


SOLUBILITY.  481 

nary  temperatuiv,  ami  the  solution  tlion  filtered,  the  filtrate  leaves 
on  spontaneous  evaporation  a  crystalline  residue  indicating  that  the 
alkaloid  requires  about  41GG  times  its  weight  of  water  for  solution. 
It  is  uiueh  more  freely  soluble  in  hot  water. 

2.  In  Chlorofoi-m. — Under  the  conditions  just  stated,  one  part 
of  mori)hine  requires  about  G550  j)arts  by  weight  of  this  fluid  for 
solution. 

3.  Ethe)\ — Under  similar  conditions,  one  part  of  the  alkaloid 
requires  7725  parts  of  absolute  ether  for  solution.  Commercial  ether 
of  specific  gravity  0.733  dissolved  one  part  of  the  alkaloid  in  4225 
parts  of  the  liquid. 

If  an  aqueous  solution  of  a  salt  of  morphine  be  decomposed  with 
slight  excess  of  sodium  carbonate,  and  the  mixture  allowed  to  repose 
for  a  little  time,  so  that  the  liberated  alkaloid  may  deposit  in  its 
crystalline  state,  and  the  whole  be  then  agitated  with  a  large  quantity 
of  absolute  ether,  this  liquid  will  take  up  only  a  mere  trace  of  the 
alkaloid,  the  proportion  being  even  much  less  than  that  stated  above. 
If,  however,  immediately  after  the  addition  of  the  sodium  carbonate, 
the  mixture  be  agitated  with  ether,  this  fluid  will  dissolve  a  much 
larger  proportion  of  the  alkaloid  than  above  stated  :  under  these 
conditions,  one  part  of  morphine  was  taken  up  by  2500  parts  of 
absolute  ether. 

4.  Alcohol. — When  excess  of  finely-pulverized  morphine  is  di- 
gested, with  frequent  agitation,  for  ten  hours  in  alcohol  of  98  per 
cent.,  the  filtered  liquid  leaves  on  spontaneous  evaporation  a  crystal- 
line residue  indicating  that  one  part  of  the  alkaloid  had  dissolved 
in  148  parts  of  the  liquid.  It  is  still  more  freely  soluble  in  hot 
alcohol ;  but  on  cooling,  the  liquid  deposits  the  greater  part  of  the 
excess  in  its  crystalline  state.  A  cold,  saturated,  alcoholic  solution 
of  the  alkaloid  has  a  well-marked  alkaline  reaction. 

5.  Alcoholic-ether. — When  twenty-five  fluid-grains  of  an  aqueous 
solution  containing  10-lOOths  of  a  grain  of  morphine  in  the  form  of 
acetate  are  treated  with  slight  excess  of  sodium  carbonate,  and  the 
whole  violently  agitated  with  jive  volumes  of  a  mixture  consisting  of 
two  parts  of  absolute  ether  and  one  part  of  pure  alcohol,  this  mix- 
ture takes  up  9-lOOths  of  a  grain  of  the  liberated  alkaloid,  which 
on  spontaneous  evaporation  it  leaves  in  the  form  of  brilliant  crys- 
tals. When  a  mixture  of  this  kind  is  agitated,  in  the  proportions 
just  mentioned,  the  alcoholic-ether  takes  up  about  one-third  of  the 

31 


482  MOEPHINE. 

aqueous  liquid,  the  original  volume  of  the  latter  being  reduced  to 
about  two-thirds. 

6.  Amyl  Alcohol. — When  excess  of  the  powdered  alkaloid  is  di- 
gested in  pure  amyl  alcohol,  with  frequent  agitation,  for  four  hours 
at  the  ordinary  temperature,  one  part  is  taken  up  by  133  parts  of 
the  menstruum. 

On  decomposing  twenty-five  grain-measures  of  an  aqueous  solu- 
tion containing  10-lOOths  of  a  grain  of  morphine  as  acetate  with 
sodium  carbonate,  and  agitating  the  mixture  with  two  volumes  and 
a  half  of  amyl  alcohol,  this  liquid  extracted  the  whole  of  the  alka- 
loid, except  the  l-200th  of  a  grain. 

7.  Pure  Acetic  Ether,  when  kept  in  contact  with  large  excess  of 
powdered  morphine  for  several  hours,  at  the  ordinary  temperature 
and  with  frequent  agitation,  dissolves  one  part  in  1030  parts  of  the 
liquid.  On  allowing  the  solution  to  evaporate  spontaneously,  the 
alkaloid  is  left  in  its  crystalline  state.  In  commercial  acetic  ether, 
which  usually  contains  alcohol  and  more  or  less  free  acetic  acid,  the 
alkaloid  is  much  more  freely  soluble,  even,  sometimes,  to  the  extent 
of  one  part  in  75  parts  of  the  fluid. 

When  half  a  grain  of  morphine,  in  the  form  of  sulphate,  was 
dissolved  in  fifty  grains  of  pure  water,  the  solution  rendered  slightly 
alkaline  by  sodium  carbonate,  and.  the  mixture  thoroughly  agitated 
with  three  volumes  of  pure  acetic  ether,  in  two  separate  portions,  this 
liquid  extracted  only  0.08  of  a  grain  of  the  liberated  alkaloid. 

The  alkaloid  is  readily  soluble  in  solutions  of  the  fixed  caustic 
alkalies;  but  only  sparingly  soluble  in  diluted  aqua  ammonise. 

The  saUs  of  morphine,  for  the  most  part,  are  readily  soluble  in 
water,  especially  if  the  liquid  be  slightly  acidulated ;  they  are  also 
soluble  in  diluted  alcohol,  but  insoluble  in  chloroform,  ether,  amyl 
alcohol,  and  pure  acetic  ether :  they  are,  therefore,  not  extracted  from 
their  aqueous  solutions  by  either  of  the  four  last-named  liquids. 
Their  aqueous  solutions,  when  pure,  are  colorless,  and  have  the  bitter 
taste  of  the  alkaloid. 

According  to  D.  B.  Dott,  the  following-named  salts' of  morphine 
are  soluble  in  the  following  proportions  respectively  of  water,  at  a 
temperature  of  15.5°  C.  (60°  F.) :  morphine  hydrochloride,  C17H19 
N03,HC1,3H20,  in  23.9  parts;  morphine  sulphate,  2C17H19NO3; 
£[2804,51120,  in  23.01  parts;  morphine  acetate,  CiyH^gN 03,0211402, 
SHgO,  2.44  parts;  morphine  tartrate,  2Ci;Hi9N03;  CJi^Oe-SR^O,  " 


SPECIAL    CHEMICAL    PROPERTIES.  483 

9.7  j)aits;  morphine  meconate,  2C,7H,9N03 ;  Cyli^O^jSHjO,  in  33.9 
parts.     {Avier.  Jour.  Phainn.,  Feb.  1883,  99.) 

Special  Chemical  Properties. — If  a  few  crystals  of  pure 
morphine  be  added  to  a  drop  or  two  of  concentrated  sulphuric  acid, 
they  slowly  dissolve  without  change  of  color,  or  at  most  yield  a 
faint  piidvish  solution.  If  a  crystal  of  potassium  dichroniate  be  now 
stirred  in  the  solution,  it  slowly  yields  green  oxide  of  chromiimi,  even 
if  oidy  the  1-lOOtli  of  a  grain  of  morphine  be  present.  If  to  the 
sulphuric  acid  solution  of  the  alkaloid  a  drop  of  potassium  dichro- 
mate  solution  be  added,  the  stirred  mixture  immediately  acquires  a 
green  coloration,  even  when  only  1-lOOOth  grain  of  the  alkaloid  is 
present.  If  a  crystal  of  potassium  nitrate  be  stirred  in  a  sulphuric 
acid  solution  of  morphine,  the  mixture  assumes  a  dark  brown  color. 

When  a  little  of  the  alkaloid  or  any  of  its  salts  is  dissolved  by 
the  aid  of  heat  in  a  small  quantity  of  concentrated  sulphuric  acid, 
and  the  solution,  after  cooling,  diluted  with  a  little  water,  and  then 
a  crystal  of  potassium  chromate  added,  the  liquid  acquires  an  in- 
tensely mahogany-brown  color  (Otto).  Under  this  treatment  the 
merest  fragment  of  morphine  will  yield  a  very  satisfactory  coloration. 

Concentrated  nitric  acid  causes  the  alkaloid  to'  assume  a  beautiful 
orange-red  color,  and  dissolves  it,  with  the  evolution  of  nitrogen  di- 
oxide (XaOo),  to  a  solution  of  the  same  hue,  which  slowly  fades  to 
yellow.  (See  post.)  The  color  of  the  nitric  acid  solution  is  not 
affected  by  chloride  of  tin.  Hydrochloric  acid  slowly  dissolves  the 
alkaloid  without  change  of  color. 

In  the  following  investigations  in  regard  to  the  reactions  of 
morphine  when  in  solution,  pure  aqueous  solutions  of  both  the  sul- 
phate and  the  acetate  were  employed.  The  fractions  indicate  the  frac- 
tional part  of  a  grain  of  anhydrous  morphine  in  solution  in  one  grain 
of  the  liquid.  When  not  otherwise  stated,  the  results  refer  to  the 
reaction  of  one  grain  of  the  solution. 

1.  Potassium  and  Sodium  Hydraies. 

The  fixed  caustic  alkalies,  when  added  in  limited  quantity,  throw 
down  from  concentrated  neutral  solutions  of  salts  of  morphine  a 
white,  amorphous  precipitate  of  the  anhydrous  alkaloid,  which  in  a 
little  time,  appropriating  a  molecule  of  water,  becomes  crystalline. 
From  more  dilute  solutions  the  precipitate  does  not  appear  until 
after  some  time,  and  it  then  separates  in  its  crystalline  form.     From 


484  MORPHLNE. 

such  solutions  the  formation  of  the  precipitate  is  much  hastened  by 
stirring  the  mixture  with  a  glass  rod.  The  precipitate  is  readily- 
soluble  in  excess  of  the  precipitant,  and  in  free  acids,  even  acetic 
acid ;  its  nitric  acid  solution  has  an  orange-red  color. 

1.  YoT  E^^'^^  of  morphine  in  one  grain  of  water  yields  with  a  small 

drop  of  the  reagent,  after  a  few  moments,  a  crystalline  precipi- 
tate, which  in  a  little  time  increases  to  a  quite  copious  deposit, 
Plate  VI.,  fig.  6.  If  on  the  addition  of  the  reagent  the  mix- 
ture be  stirred  with  a  glass  rod,  it  immediately  yields  streaks  of 
crystals  along  the  path  of  the  rod,  over  the  bottom  of  the  watch- 
glass  containing  the  mixture,  and  in  a  few  moments  there  is  a 
very  copious  crystalline  deposit.  Since  the  precipitate  is  readily 
soluble  in  the  fixed  caustic  alkalies,  care  should  be  taken  to 
avoid  the  addition  of  much  excess  of  the  reagent,  otherwise  no 
deposit  will  form. 

2.  -g-^  grain  yields  after  a  little  time,  by  stirring  the  mixture,  a 

very  good  deposit. 

3.  Y^oT   gi'^i^  •    when    the    least   possible    quantity    of   reagent   is 

employed,  the  mixture  yields  after  a  time  a  Cjuite  satisfactory 

granular  precipitate. 
These  reagents  also  produce  in  solutions  of  most  of  the  other  alka- 
loids white,  crystalline  precipitates;  but  the  crystalline  form  of  the 
morphine  deposit,  when  from  not  too  dilute  solutions,  is  somewhat 
peculiar.  Its  true  nature  may  be  fully  established  by  its  behavior 
with  nitric  acid  or  some  of  the  other  tests  mentioned  hereafter. 

2.  Ammonia. 

Ammonia  produces  with  neutral  solutions  of  salts  of  morphine 
much  the  same  results  as  tlie  fixed  caustic  alkalies;  but  the  pre- 
cipitate is  not  so  readily  soluble  in  excess  of  the  precipitant.  From 
dikite  solutions,  therefore,  it  is  much  more  easy  to  obtain  precipitates 
by  this  reagent  than  by  either  potassium  or  sodium  hydrate.  If  a 
drop  of  a  solution  of  the  alkaloid  be  exposed  to  the  vapor  of  a 
drop  of  ammonia  suspended  on  a  glass  rod,  it  yields  after  a  little 
time  a  white,  crystalline  deposit.  .  This  is  much  the  best  method  for 
obtaining  precipitates  from  very  dilute  solutions  of  the  alkaloid. 

The  alkali  carbonates,  also,  throw  down  from  normal  solutions  of 
salts  of  morphine  a  white  precipitate  of  the  alkaloid,  which  is  only 
very  sparingly  soluble  in  large  excess  of  the  precipitant.     If,  how- 


NITUIC   ACID   TKST.  485 

ever,  lt\ri;e  excess  of  the  reagent  be  added  at  first,  the  forniation  of 
the  precipitate  is  partially  or  entirely  [)ri;vented.  The  limit  of  the 
reaction  of  these  reagents  is  the  same  as  that  of  the  caustic  alicalies. 

3.  Nitric  Acid. 

When  somewhat  strong  solutions  of  salts  of  morphine  are  treated 
with  large  excess  of  concentrated  nitric  acid,  the  mixture  slowly 
acquires  a  lemon-yellow  or  orange-red  color,  its  exact  tint  depending 
upon  the  relative  proportion  of  acid  and  morphine  present. 

1.  YTH  grain  of  morphine,  in  one  grain  of  water,  yields,  with  a  few 

drops  of  the  acid,  a  yellow  solution,  which  very  soon  acquires 
an  orange  color,  then  a  deep  orange-red,  after  whicli  the  liquid 
slowly  becomes  again  yellow. 

2.  y^Vd  gi'aiu  :  the  mixture  slowly  acquires  a  lemon  color,  which 

after  some  minutes  becomes  light  orange. 

3.  -s^-^jTi)  g''ain  :  after  some  minutes  the  mixture  assumes  a  quite  per- 

ceptible lemon  hue,  which  is  best  seen  over  a  white  ground. 
The  reaction  of  this  test  is  much  more  satisfactory  and  delicate 
when  a  small  portion  of  the  acid  is  applied  to  the  alkaloid,  or  to  any 
of  its  salts  in  the  dry  state. 

1.  y-J-jj  grain  of  morphine — in  the  form  of  sulphate  or  acetate,  as 

left  upon  evaporating  one  grain  of  its  aqueous  solution  to  dry- 
ness— when  touched  with  a  small  drop  of  nitric  acid,  almost 
immediately  assumes  a  fine  orange-red  color,  and  dissolves  to  a 
solution  of  the  same  hue,  which  slowly  fades  to  yellow. 

2.  Yoinr  grain :  at  first  the  deposit  assumes  a  yellow  color,  which, 

however,  soon  changes  to  a  bright  brownish-orange,  and  dis- 
solves to  a  fine  orange  solution. 

3.  ^-gVo  gi'ain  :  the  residue  assumes  a  very  distinct  brown  color,  and 

dissolves  to  a  faint  brownish  solution. 

4.  YTj-.-o-oo"  grain,  when  touched  with  a  very  minute  quantity  of  the 

acid,  after  a  little  time  acquires  a  very  faint  brownish  hue. 
Brucine,  and  strychnine  containing  this  alkaloid,  immediately 
strike  a  deep  blood-red  or  bright  red  color  when  treated  with  strong 
nitric  acid.  This  color,  however,  upon  the  addition  of  a  solution 
of  tannous  chloride,  is  changed  to  bright  purple;  whereas  that 
produced  from  morphine  is  unaffected,  or,  at  most,  is  changed  to 
yellow,  by  this  reagent.  Nitric  acid  also  produces  a  more  or  less 
red  coloration  with  certain  volatile  oils  and  resinous  substances,  but 


486  MORPHINE. 

none  of  these  are  crystallizable,  in  which  respect  [^they  differ  from 
morphine. 

4.  Iodic  Add. 

When  a  tolerably  strong  solution  of  a  salt  of  morphine,  or  the 
alkaloid  or  any  of  its  salts  in  the  dry  state,  is  treated  with  a  strong 
solution  of  iodic  acid,  the  latter  is  decomposed,  with  the  elimination 
of  free  iodine,  which  falls  as  a  brown  or  reddish-brown  precipitate, 
and  the  mixture  emits  the  odor  of  iodine.  If  a  freshly  prepared 
solution  of  starch-paste  be  now  added,  the  mixture  acquires  a  blue 
color,  due  to  the  formation  of  iodide  of  starch.  For  the  production 
of  this  blue  color,  however,  it  is  necessary,  as  pointed  out  by  M. 
Dupre  {Chemical  News,  Dec.  1863,  267),  that  the  proportions  of  iodic 
acid  and  starch  employed  be  within  certain  limits,  since  the  color  is 
destroyed  by  large  excess  of  iodic  acid,  and  also  by  large  excess  of 
the  starch  solution. 

1.  yi-^  grain  of  morphine,  in  one  grain  of  water,  when  treated  in 

the  above  manner,  yields  a  blue  precipitate  and  imparts  a  deep 
blue  color  to  the  liquid. 

2.  3^   grain  yields  a  brownish  liquid,  and-  a  quite  distinct  blue 

precipitate. 

3.  yfW  E^^^^  '•  ^^^^  mixture  assumes  a  slight  brownish  color,  but  it 

fails  to  yield  a  precipitate. 

This  reaction  is  much  more  delicate  when  applied  to  morphine 
or  any  of  its  salts  in  the  solid  state.  For  this  purpose,  as  advised 
by  M.  Dupr§,  the  morphine  or  its  solution  is  first  treated  with  a  drop 
of  starch  solution ;  the  mixture  is  then  carefully  evaporated  to  dry- 
ness, and  the  residue,  after  cooling,  moistened  with  a  solution  of  iodic 
acid.  In  this  manner  a  residue  containing  only  the  l-10,000th  of 
a  grain  of  the  alkaloid  will  yield  a  quite  distinct  blue  color. 

The  reactions  of  this  test  are  common  to  many  other  substances, 
some  of  which,  like  morphine,  are  crystallizable. 

M.  Lefort  has  recommended  to  treat  the  mixture  of  morphine 
and  iodic  acid  with  ammonia  instead  of  starch,  by  which  the  yellow 
color  of  the  mixture  is  changed  to  deep  brown  or  yellowish-brown. 
In  applying  this  method  to  dilute  solutions  of  the  alkaloid,  the 
iodic  acid  mixture  should  be  allowed  to  stand  some  minutes  before 
the  ammonia  is  added,  since  otherwise  the  coloration  may  be  entirely 
prevented. 


FERRIC   CHLORIDK   TKST.  487 

This  method,  when  applied  to  solutions,  is  miieh  more  delicate 
than  the  starch  process  before  described;  and,  moreover,  it  is  said 
that  tlie  yellow  color  produced  by  iodic  acid  with  most  other  sub- 
stances capable  of  reducing  this  acid  is  dischari^ed  by  ammonia, 
whereby  morphine  may  be  distinguished  from  such  substances.  For 
the  detection  of  morphine  in  highly  diluted  solutions,  the  author 
of  this  method  advises  to  moisten  slips  of  unsized  paper  repeatedly 
with  the  alkaloidal  solution,  carefully  drying  them  between  each  im- 
mersion, and  then  apply  the  iodic  acid  solution  and  ammonia  to  the 
paper  thus  prepared. 

Another  method  for  detecting  tlie  eliminated  iodine  is  by  means 
of  carbon  disulphkle,  which  will  dissolve  it  with  a  more  or  less 
marked  color.  For  this  purpose,  a  few  drops  of  a  strong  solution 
of  iodic  acid  are  agitated  in  a  small  test-tube  with  an  equjl  volume 
of  carbon  disulphide,  and  then,  if  no  coloration  is  produced,  a  small 
portion  of  the  alkaloid  or  of  its  saline  solution  is  added  and  the 
mixture  again  agitated,  Avhen,  on  repose,  the  disulphide  liquid  will 
subside  and  present  a  color  varying  from  a  faint  light  pink  to  deep 
dark  red,  depending  upon  the  quantity  of  morphine  present. 

In  this  manner,  1-lOOth  grain  of  morphine  will  yield  a  deep 
pink  coloration,  which  is  quickly  discharged  by  a  cirop  of  ammonia. 
One  drop  of  a  l-oOOOth  solution  of  the  alkaloid  will  cause  a  dis- 
tinctly marked  pinkish  hue.  This  method  is  open  to  the  same 
fallacies  as  the  starch  reaction. 

5.  Ferric  Chloride. 

Concentrated  solutions  of  salts  of  morphine,  as  well  as  the 
alkaloid  or  any  of  its  salts  in  the  solid  state,  strike  with  a  neutral 
solution  of  ferric  chloride,  or  of  ferric  sulphate,  providing  no  free 
acid  is  present,  a  deep  blue  color,  which  is  discharged  by  free  acids, 
by  the  caustic  alkalies,  and  by  heat.  On  the  addition  of  nitric  acid 
the  blue  mixture  acquires  an  orange-red  color. 
^-  ToT  gi'ain  of  morphine,  in  solution  in  one  grain  of  water,  yields 

with  a  drop  of  the  reagent  a  quite  good,  ink-blue  coloration. 
2-  T(hr  gi'ain :  after  a  ^ew  minutes  the  reaction  is  evident,  but  not 
satisfactory. 

The  reaction  of  this  reagent  is  much  more  delicate  when  applied 
to  morphine  in  its  solid  state.  Thus,  if  a  drop  of  the  reagent  be 
flowed  over  a  1-lOOOth  grain  residue  of  the  alkaloid,  it  will  yield 


488  MOEPHINE. 

a  deep  blue  color;  and  even  with  the  l-10,000th  of  a  grain  the 
reaction  is  still  quite  marked. 

Ferric  chloride  also  occasions  with  tannic  and  gallic  acids  a  blue 
color,  which  is  changed  to  reddish-yellow  by  nitric  acid.  When 
either  of  these  vegetable  acids  is  treated  with  nitric  acid  alone,  it 
yields  a  yellow  solution ;  in  this  respect  they  differ  from  morphine. 
There  are  also  some  few  vegetable  infusions  which,  when  treated 
with  a  ferric  salt,  give  rise  to  a  more  or  less  blue  coloration.  On 
the  other  hand,  it  should  be  borne  in  mind  that  the  blue  color  pro- 
duced by  morphine  may  not  make  its  appearance  if  the  alkaloid  be 
mixed  with  certain  foreign  substances. 

If  a  few  drops  of  a  solution  of  morphine  be  treated  with  a  drop 
or  two  of  a  neutral  solution  of  ferric  chloride,,  and  then  a  drop  of  a 
dilute  solution  of  potassium  ferricyanide  be  added,  the  latter  salt  is 
reduced  by  the  alkaloid  to  potassium  ferrocyanide,  which,  reacting 
on  the  ferric  salt,  produces  Prussian  blue,  which  imparts  a  deep  blue 
color  to  the  mixture.  In  this  manner  a  1-lOOOth  solution  of  mor- 
phine will  yield  an  intense  deep  blue  mixture ;  a  1-1 0,000th  solu- 
tion, a  clear  blue  color ;  and  a  l-50,000th  solution,  a  strongly  marked 
green  coloration. 

According  to  M.  Kieffer,  who  first  advised  this  test,  the  reaction 
is  not  interfered  with  by  heat,  nor  by  free  acids  in  moderate  quantity ; 
but  excess  of  an  alkali  prevents  it  by  acting  upon  the  ferric  salt. 
Neither  is  the  test  interfered  with  by  the  presence  of  gum,  sugar^ 
alcohol,  glycerine,  quinine,  or  atropine.  We  find,  however,  that  the 
same  reaction  is  produced  by  brucine,  and  by  narcotine,  and  also  by 
sulphites  and  similar  reducing  agents ;  but  not  by  strychnine,  papa- 
verine, or  meconin. 

6.  Sulpho-Molybdic  Acid. 
When  morphine  in  its  solid  state,  or  any  of  its  salts,  is  touched 
with  a  drop  of  sulphuric  acid  containing  a  little  molybdic  acid,  it 
immediately  dissolves,  with  the  production  of  a  beautiful  purple  or 
crimson  color,  which  quickly  passes  through  several  shades,  and  after 
a  time  the  mixture  acquires  a  deep  blue  color,  which  generally  appears 
first  along  the  margin  of  the  liquid  and  is  more  or  less  permanent. 
Sometimes  the  final  color  is  green  or  brownish-green,  or  it  may  be 
yellow.     This  reaction  was  first  observed  by  M.  Froehde,  in  1866. 

The  reagent  may  be  prepared  by  dissolving  three  parts  of  mo- 
lybdic acid,  or  of  an  alkali  molybdate,  in  100  parts  of  pure  sulphuric 


SULPIIO-MOLYRDIC    ACID   TEST.  489 

acid,  by  the  aid  of  a  moderate  heat.  Froehde  advised  to  dissolve 
five  milligrammes  of  the  molybdie  compound  in  one  cubic  centimetre 
of  sulphuric  acid  (one  part  in  368  of  acid).  The  reagent  should  l)e 
freshly  prepared  when  required  for  use. 

The  exact  nature  of  the  reaction  of  this  test  is  yet  not  fully 
understood.  It  is  known,  however,  that  in  the  final  result  a  portion 
at  least  of  the  molybdic  acid  is  reduced,  a  lower  oxide  of  the  metal 
being  formed.  The  final  blue  color  is  discharged  by  hydrochloric 
acid  and  by  free  chlorine;  also  by  nitric  acid,  which,  when  the  mor- 
phine is  present  in  not  too  minute  quantity,  changes  it  to  a  reddish 
or  orange-red  hue. 

1.  j-Q-jj  grain  of  morphine,  as  sulphate,  in  the  dry  state,  when  treated 

with  a  moderate  drop  of  the  reagent,  yields  an  immediate,  intense 
purple  coloration.  After  one  or  two  minutes  the  drop  acquires 
a  deep  blue  color  along  the  margin,  and  soon  the  whole  liquid 
assumes  a  deep  blue  color,  which  is  permanent  for  at  least  some 
days. 

2.  YTWo  gr^in?  ^'ith  a  minute  drop  of  the  reagent,  yields  much  the 

same  results  as  1.  If  the  mixture  be  stirred,  the  blue  color 
may  quickly  disappear. 

3.  Yo.Wo"  grain :  a  fine  purple  coloration,  which  after  a  little  time 

disappears,  and  the  liquid  acquires  a  yellow  hue.  If  the  mor- 
phine residue  be  only  moistened  with  the  reagent,  the  purple 
color  is  soon  changed  into  blue,  which  remains  unchanged  for 
half  an  hour  or  longer. 

4.  g-g-.ouo"  grain:  if  a  minute  drop  of  the  reagent  be  flowed  over 

the  deposit,  a  very  marked  purple  coloration  manifests  itself 
along  the  lines  of  the  deposit ;  after  a  little  time  this  color 
disappears,  the  liquid  becoming  colorless. 

5.  YoXTToo"  grain,  treated  as  in  4,  yields  a  distinct  purple  coloration, 

which  quickly  disappears. 
The  reaction  of  this  test,  like  that  of  the  color-test  for  strych- 
nine, with  which  it  is  very  analogous,  will  reveal  itself  with  about  the 
least  quantity  of  morphine  visible  to  the  naked  eye,  and,  when  the 
test  is  performed  under  the  microscope,  with  about  the  least  crystal 
visible  under  a  low  power  of  the  instrument.  The  reaction  is  pro- 
duced by  morphine  and  its  ordinary  salts,  but  when  present  in  only 
very  minute  quantity  the  reaction  of  the  free  alkaloid  and  its  sul- 
phate is  more  satisfactory  than  that  of  the  acetate  and  hydrochloride. 


490  MORPHINE. 

Fallacies. — Sulpho-molybdic  acid  produces  a  similar  violet  or 
purple  coloration  with  papaverine,  salicin,  and  populin.  These  sub- 
stances, however,  differ  from  morphine  in  that  when  treated  with 
sulphuric  acid  alone,  papaverine  dissolves  with  a  purple  or  violet 
color,  and  salicin  and  populin  strike  a  red  coloration ;  whereas 
morphine,  when  pure,  dissolves  without  color. 

Various  alkaloids  and  similar  principles  will  yield  under  the 
action  of  this  reagent,  either  immediately  or  after  a  time,  a  more  or 
less  blue,  green,  brown,  or  yellow  coloration  ;  and  even  ordinary 
organic  matter  may  after  a  time  cause  a  blue  color.  These  results, 
however,  could  not  be  confounded  with  the  morphine  reaction. 
Strychnine  yields  no  coloration  with  the  reagent. 

7.  Potassium  Iodide. 

This  reagent  produces  in  somewhat  concentrated  neutral  solutions 
of  salts  of  morphine,  especially  if  the  mixture  be  stirred  or  allowed 
to  stand  some  time,  a  white,  crystalline  precipitate,  which  is  readily 
soluble  in  acids',  even  acetic  acid.  This  reaction  is  readily  interfered 
with  by  the  presence  of  foreign  substances. 

1.  YTo    gi'^i^i  of  morphine,  in   one  grain   of  water,  yields  after  a 

little  time  a  quite  copious  deposit  of  large  groups  of  crystalline 
needles,  Plate  VII.,  fig.  1.  The  precipitate  from  a  solution 
of  the  sulphate  of  morphine  is  more  prompt  in  forming,  and 
somewhat  more  abundant,  than  that  obtained  from  the  acetate. 

2.  5^  grain  yields  after  some  minutes  a  very  good,  granular  deposit. 
This  reagent  also  produces  white  crystalline  precipitates  with 

several  of  the  alkaloids,  but  the  forms  of  these  in  most  instances 
differ  widely  from  those  obtained  from  morphine. 

8.  Potassium  Chromate. 

Potassium  chromate  throws  down  from  strong  neutral  solutions 
of  salts  of  morphine  a  yellow,  crystalline  precipitate,  which  is  very 
readily  soluble  in  free  acids. 

1.  YFo"  grain  of  morphine  yields  in  a  very  little  time,  especially  if 

the  mixture  be  stirred,  a  very  copious,  crystalline  deposit,  having 
the  forms  illustrated  in  Plate  VII.,  fig.  2. 

2.  iQQQ  grain  yields  after  some  time  a  slight  granular  precipitate. 
Potassium  dichromate  produces  in  one  drop  of  a  1— 100th  solution 

of  the  alkaloid  a  yellow,  amorphous  precipitate,  which  after  a  time 


AURIC   CHLORIDE   TEST.  491 

becomes  granular.     In  solutions  but  little  more  dilute  than  this  the 
reagent  fails  to  produce  a  precipitate. 

9.  Auric  Chloride. 

Solutions  of  salts  of  nioriiliine  yield,  with  trichloride  of  gold, 
a  bright  yellow,  amorphous  precipitate,  which  almost  immediately 
begins  to  darken,  becoming  bluish  and  finally  dirty  green  or  nearly 
black.  Solutions  of  the  sulphate  of  morphine  do  not  seem  to  undergo 
this  change  as  rapidly  as  those  of  the  acetate.  The  precipitate  is  par- 
tially soluble  in  acetic  and  nitric  acids.  If  the  precipitate,  as  first 
produced,  be  treated  with  a  solution  of  potassium  hydrate,  it  imme- 
diately darkens,  and  the  mixture  becomes  bluish,  purplish,  or  nearly 
black,  its  exact  color  depending  upon  the  relative  quantity  of  reagent 
employed. 

1.  ^  grain    of  morphine,  in  one  grain  of  water,  yields   a  very 

copious,  yellow  deposit,  which  undergoes  the  changes  above 
described. 

2.  ^.^  grain  yields  after  a  few  moments  a  very  good,  yellow  pre- 

cipitate, which  slowly  darkens.  When  treated  with  a  drop  of 
potassium  hydrate  solution,  the  precipitate  dissolves,  and  the  mix- 
ture, in  a  very  little  time,  becomes  purplish  or  nearly  black. 

3.  y^JLj-g-g-  grain:   after  a  little  time  a  good  precipitate,  which   is 

readily  soluble,  to  a  clear  solution,  in  potassium  hydrate.  After 
some  minutes,  however,  the  alkaline  mixture  deposits  small 
black  flakes. 

4.  ^3--i^pj-  grain  yields,  after  standing  some  time,  a  quite  distinct 

turbidity. 

If  the  precipitate  from  ten  or  fifteen  grains  of  a  1-lOOOth  or 
stronger  solution  of  the  alkaloid  be  boiled  in  the  mixture,  the  deposit, 
without  dissolving,  assumes  a  brown  or  dark  color,  due  to  its  partial 
decomposition;  the  deposit  from  a  l-2500th  solution  readily  dis- 
solves upon  heating,  and  the  mixture  on  cooling  immediately  darkens, 
from  the  presence  of  small  black  flakes,  which  after  a  time  adhere 
to  the  sides  of  the  tube ;  the  ])recipitate  from  a  l-5000th  solution 
readily  dissolves  by  heat,  yielding  a  yellow  solution,  which  under- 
goes but  little  change,  even  after  several  hours. 

Besides  morphine,  tannic  and  gallic  acids  and  certain  other  organic 
substances  have  the  property  of  precipitating  and  reducing  solutions 
of  salts  of  gold.     With  the  aid  of  potassium  hydrate  most  organic 


492  MOEPHINE. 

compounds  precipitate  the  metal  in  the  form  of  a  black  powder; 
and  even  a  mixture  of  chloride  of  gold  and  potassium  hydrate  alone 
may  after  a  time  yield  black  flakes. 

10.  Platinie  Chloride. 

This  reagent  throws  down  from  concentrated  neutral  solutions  of 
acetate  of  morphine  a  yellow,  granular  precipitate,  which  is  very 
readily  soluble  in  acids,  even  acetic  acid. 

One  grain  of  a  1-lOOth  solution  of  the  alkaloid  yields,  especially 
if  the  mixture  be  allowed  to  stand  some  time,  a  quite  good,  yellow 
deposit,  Plate  VII.,  fig.  3.  Solutions  but  little  more  dilute  than  this 
fail  to  yield  a  precipitate. 

11.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  produces  in  solutions  of 
salts  of  morphine,  even  when  highly  diluted,  a  reddish-brown  amor- 
phous precipitate,  which  is  but  slowly  soluble  in  acetic  acid,  but  dis- 
solves readily  to  a  clear  solution  in  potassium  hydrate ;  it  is  also 
soluble  in  alcohol.  Unless  large  excess  of  the  reagent  be  added,  the 
precipitate  after  a  time  partially  or  entirely  disappears.  The  reagent 
may  be  prepared  by  dissolving  two  parts  of  iodine  and  five  parts  of 
potassium  iodide  in  100  parts  of  water. 

1.  Y^-g-  grain  of  morphine,  in    one   grain    of  water,  yields  a  very 

copious  deposit. 
After  a  few  minutes  the  precipitate  assumes  a  lighter  color, 
becomes  granular,  and  soon  twig-like  groups  of  crystals  or  plates 
appear,  having  various  colors,  being  either  orange-red,  brown,  yellow, 
or  nearly  black,  Plate  XIV.,  fig.  1.  The  formation  of  the  crystals 
is  much  facilitated  by  stirring  the  mixture ;  and  they  are  more 
readily  obtained  from  the  acetate  and  hydrochloride  of  morphine 
than  from  the  sulphate.  The  presence  of  a  trace  of  free  acetic  acid 
also  promotes  their  formation, 

2.  YFU~o  gi^"ain  :  a  very  good  reddish-brown  precipitate.    After  a  time, 

especially  if  the  mixture  be  stirred,  beautiful  groups  of  reddish- 
brown  crystals  may  appear. 

3.  To".Wo  g'^aiQ :  an  immediate  turbidity,  and  in  a  little  time  a  very 

fair,  brownish-yellow  deposit,  which  may  become  more  or  less 
crystalline. 

4.  -g-Q-.ToT  grain  yields  a  very  satisfactory  turbidity. 


CIILOKINE    AND    AMMONIA    TEST.  493 

The  production  of  a  precipitate  by  this  reagent  is  common  to  a 
large  class  of  organic  substances;  yet  the  character  of  the  crystals, 
when  obtained,  is  rather  peculiar  to  morphine.  Codeine  yields  with 
the  reagent  somewhat  similar  crystals.  The  formation  of  the  mor- 
phine crystals  is  readily  prevented  by  the  presence  of  foreign  matter. 

12.  Bromine  in  Bromohydric  Acid. 

Neutral  solutions  of  salts  of  morphine,  when  treated  with  a  so- 
lution of  bromohydric  acid  saturated  with  bromine,  yield  a  yellow, 
amorjihous  precipitate,  which  after  a  time  dissolves,  but  is  reproduced 
upon  further  addition  of  the  reagent.  The  precipitate  is  soluble  in 
acetic  acid  and  in  alcohol. 

1.  YTW  g'''^i"  of  morphine  yields  a  very  copious  precipitate,  which 

remains  amorphous. 

2.  YoW  grain  :  a  quite  good  deposit. 

3.  ■sVg-jj-  grain  yields  a  slight  turbidity. 

This  reagent  also  produces  similar  precipitates  with  various  other 
organic  substances. 

13.  Picric  Acid. 

An  alcoholic  solution  of  picric  acid  produces  in, aqueous  solutions 
of  salts  of  morphine  a  bright  yellow,  amorphous  precipitate,  which 
is  readily  soluble  in  alcohol,  but  only  slowly  soluble  in  acetic  acid. 
The  precipitate  remains  amorphous. 

1.  Yoo"  gi'^i"    of  morphine,  in  one  grain    of  water,  yields  a  very 

copious  deposit. 

2.  -g-^^  grain  yields  a  quite  distinct  precipitate. 

3.  YxrVo  g^'^in  •  DO  indication. 

This  reaction  is  common  to  a  great  number  of  organic  substances, 
but  with  several  of  the  other  alkaloids  the  reagent  produces  crystal- 
line precipitates. 

14.   Oilorine  and  Ammonia. 

When  a  strong  solution  of  a  salt  of  morphine  is  treated  with  a 
slow  stream  of  chlorine  gas,  it  acquires  a  deep  yellow  color,  which, 
upon  the  addition  of  ammonia,  is  changed  to  deep  brown.  This 
color  is  not  affected  by  large  excess  of  ammonia  or  by  acetic  acid. 
1.  1-lOOth  solution  of  morphine  :  ten  grains  of  this  solution  yield 
results  similar  to  those  just  described. 


494  MORPHINE. 

2.  1-lOOOth  solution :  chlorine  imparts  to  the  liquid  a  yellow  tint, 
which  is  changed  to  a  quite  distinct  brownish  hue  by  ammonia. 
Solutions  but  little  more  dilute  than  the  last-named  show  no 
change  when  treated  with  these  reagents. 

Other  Reagents. — Potassium  iodoliydrargyrate,  or  a  solution  of 
corrosive  sublimate  containing  just  sufficient  potassium  iodide  to  re- 
dissolve  the  precipitate  first  produced,  produces  in  solutions  of  salts 
of  morphine,  even  when  highly  diluted,  a  dirty-white,  gelatinous  or 
flocculent  precipitate  of  the  double  iodide  of  morphine  and  mercury, 
which  is  only  very  sparingly  soluble  in  diluted  acetic  and  hydro- 
chloric acids,  but  readily  soluble  in  large  excess  of  alcohol. 

The  precipitate  thus  produced,  especially  when  from  somewhat 
dilute  solutions  of  morphine,  after  a  little  time  becomes  in  part  or 
Avholly  converted  into  groups  or  bundles  of  fine,  delicate,  crystalline 
needles.  In  this  manner  the  l-lOOOth  grain  of  morphine  will  yield 
a  very  good  crystalline  deposit,  Plate  XIV.,  fig.  2.  A  drop  of  a 
1— 10,000th  solution  of  the  alkaloid  yields  no  immediate  precipitate 
with  the  reagent,  but  after  a  time  very  long  slender  needles  appear. 

The  production  of  a  white  or  dirty-white  precipitate  by  this 
reagent  is  common  to  a  large  number  of  organic  principles;  and  in 
some  instances,  as  in  the  present,  the  precipitate  becomes  more  or  less 
crystalline. 

Tannic  acid  throws  down  from  somewhat  strong,  neutral  solu- 
tions of  salts  of  the  alkaloid  a  white,  flocculent  precipitate,  wdiich  is 
readily  soluble  in  acids  and  in  the  fixed  caustic  alkalies.  Palladium 
chloride  produces  in  similar  solutions  a  yellow,  amorphous  precipi- 
tate, which  is  also  readily  soluble  in  acids. 

When  a  few  drops  of  a  strong  solution  of  a  salt  of  morphine 
are  treated  with  a  strong  solution  of  silver  nitrate,  the  latter  salt, 
especially  if  the  mixture  be  gently  heated,  is  sooner  or  later  decom- 
posed, with  the  production  of  a  shining,  crystalline  precipitate  of 
metallic  silver;  at  the  same  time,  the  mixture  acquires  a  more  or  less 
yellow  hue,  due  to  the  action  of  the  eliminated  nitric  acid  upon  the 
alkaloid.  (J.  Horsley,  Chem.  News,  July,  1862,  6.)  One  grain  of  a 
1-lOOth  solution  of  morphine,  when  treated  after  this  method,  yields 
a  very  satisfactory  deposit. 

As  a  test  for  morphine,  A.  Jorissen  has  advised  to  heat  the  alka- 
loid with  a  few  drops  of  pure  sulphuric  acid  on  a  water-bath,  then 


MECONIC   ACID.  495 

add  Ji  niimitc  crystal  of /e/Tojw  sufplKilc,  si'iv  tlie  cnislicd  crystal  in 
the  liquid,  and  continue  the  heat  lor  ahout  a  minute.  Tlie  solution 
is  then  poured  into  a  porcelain  capsule  containing  a  little  strong  am- 
monia, when  the  morphine  solution  will  assume  a  red  color,  passing 
into  violet  at  the  margin,  whilst  the  ammoniacal  stratum  will  acquire 
a  deep  blue  color.  {Chcm.  News,  Feb.  1882,  57.)  1-lOOth  grain  of 
morphine  will,  in  this  manner,  produce  a  marked  coloration.  Code- 
ine lails  to  respond  to  this  reaction. 

When  a  little  mori)hiue  is  treated  with  a  drop  of  concentrated 
sulphuric  acid  holding  in  solution  titanic  acid,  a  red-hrown  color, 
passing  to  violet,  is  produced. 

Potassium  sulphocyanide,  ferrocyanide,  and  ferricyanide,  also  lead 
acetate  and  barium  chloride,  fail  to  produce  a  j)recipitate,  even  in 
concentrated  solutions  of  salts  of  morphine,  at  least  so  far  as  the 
alkaloid  itself  is  concerned. 

Among  the  tests  now  described  for  the  detection  of  morphine, 
the  reaction  of  no  one  of  them,  taken  alone,  as  already  intimated,  is 
peculiar  to  the  alkaloid.  But  by  the  concurrent  action  of  two  or 
more  of  them,  especially  the  sulpho-molybdic  acid,  nitric  acid,  and 
ferric  chloride  tests,  the  true  nature  of  even  exceedingly  minute  quan- 
tities of  the  alkaloid  may  be  fully  established,  especially  if  it  be  in 
the  crystalline  state.  It  may  here  be  remarked  that  of  the  ordinary 
alkaloids  morphine  is  one  of  the  most  difficult  to  recover,  especially 
in  its  pure  state,  from  complex  organic  mixtures. 

III.  Meconic  Acid. 

History. — Meconic  acid  was  discovered,  in  1804,  by  Sertiirner. 
In  its  pure  state  it  crystallizes  in  the  form  of  colorless  plates,  either 
singly  or  in  groups;  its  composition  in  this  form  is  HgC^HO^jSHgO. 
In  nature  it  has  been  found  only  in  the  poppy  tribe,  in  which  it  exists 
as  meconate  of  morphine.  Of  good  Smyrna  opium  it  forms  about 
six  per  cent. ;  its  proportion,  however,  varies  in  different  samples  of 
the  drug,  and  it  is  even  said  to  be  sometimes  altogether  absent ;  but 
this  statement  is  exceedingly  doubtful. 

Pveparalioii. — Various  methods  have  been  proposed  for  the  prep- 
aration of  meconic  acid,  but  we  have  found  the  following  to  be  one 
of  the  most  simple,  at  least  if  only  a  small  quantity  of  the  substance 


496  MECONIC   ACID. 

be  desired.  A  strong  filtered  aqueous  solution  of  opium  is  treated 
with  excess  of  lead  acetate,  and  the  impure  meconate  of  lead  thus  pro- 
duced collected  on  a  filter  and  washed,  as  long  as  the  washings  become 
colored.  It  is  then  diffused  in  a  small  quantity  of  water  and  treated 
with  excess  of  sulphuretted  hydrogen  gas,  whereby  the  lead  is  pre- 
cipitated as  sulphide,  while  the  liberated  meconic  acid  enters  into  so- 
lution. The  liquid  is  now  filtered  and  evaporated  on  a  water-bath 
at  a  very  moderate  heat,  until  a  drop  of  it  removed  to  a  watch-glass, 
cooled,  and  stirred  with  a  drop  of  hydrochloric  acid,  yields  a  crys- 
talline precipitate.  The  liquid  is  then  allowed  to  cool,  and  strongly 
acidulated  with  pure  hydrochloric  acid,  when  after  a  time  the  me- 
conic acid,  being  insoluble  in  diluted  hydrochloric  acid,  will  separate 
in  the  form  of  shining  plates  and  crystalline'  groups.  Should  the 
crystals  not  be  entirely  colorless,  they  may  be  redissolved  in  a  small 
quantity  of  hot  water,  and  the  cooled  solution  again  strongly  acidu- 
lated with  hydrochloric  acid. 

Physiological  Effects. — Meconic  acid,  when  taken  into  the  system, 
seems  to  be  inert.  At  least,  it  has  repeatedly  been  administered  to 
inferior  animals  in  doses  of  several  grains,  and  taken  by  man  in 
similar  quantities,  without  producing  any  appreciable  effect. 

General  Chemicae  Natuee.— As  usually  found  in  the  shops, 
meconic  acid  is  in  the  form  of  crystalline  scales,  having  a  more  or 
less  reddish  color,  due  to  the  presence  of  foreign  matter.  It  has  an 
acid,  astringent  taste,  and  strongly  acid  properties,  readily  uniting 
with  the  metals,  forming  salts  called  meconates.  It,  like  phosphoric 
and  arsenic  acids,  is  tribasic,  or  capable  of  uniting  with  three  atoms 
of  a  raonatomic  metal.  When  the  crystallized  acid  is  heated,  it  first 
parts  with  its  three  molecules  of  water  of  crystallization,  then  fuses, 
emits  dense,  white  fumes,  and  finally  takes  fire,  burning  with  a  yellow 
flame.  If  the  acid  be  moderately  heated  in  a  reduction-tube,  it  some- 
times yields  a  sublimate  of  crystalline  needles. 

Solubility. — Meconic  acid  is  soluble  in  about  one  hundred  and 
fifteen  times  its  weight  of  pure  water,  at  a  temperature  of  15.5°  C. 
(60°  F.),  forming  a  strongly  acid  solution.  It  is  much  more  freely 
soluble  in  hot  water,  from  which,  however,  much  of  the  excess  sep- 
arates, in  the  crystalline  form,  as  the  solution  cools.  In  water  con- 
taining free  hydrochloric  acid,  meconic  acid  is  very  much  less  soluble 
than  in  pure  water.  Alcohol  dissolves  it  rather  freely,  and  leaves  it, 
on  spontaneous  evaporation  of  the  liquid,  in  the  form  of  beautiful 


SPECIAL   CHEMICAL   PROPERTIES.  497 

groups  of  crystals.  It  is  only  very  sj)aringly  soluble  in  absolute 
ethir,  rcqiiiriui^r  about  2150  parts  by  weigbt  of  ibis  liquid  for  solu- 
tion ;  ami  it  is  almost  wliolly  insoluble  in  chloroform.  Tlic  huUh  of 
tbis  acid,  except  tliose  of  the  alkalies,  which  are  freely  soluble,  are, 
for  the  most  part,  insoluble  in  water.  They  are  also  insoluble,  or 
very  nearly  so,  in  alcohol. 

Special  Chemical  Properties.— Meconic  aeid,  in  its  solid 
state,  is  unchanged  in  eolor  by  cold  sulphuric,  nitric,  and  hydrochloric 
acids.  On  the  application  of  a  very  gentle  heat,  it  dissolves  quietly 
to  a  clear  solution  in  the  first  two  of  these  mineral  acids,  but  it  is 
insoluble  in  hydrochloric  acid ;  at  a  little  higher  temperature  it  is 
readily  decomposed  by  the  mineral  acids  with  effervescence.  When 
heated  to  a  temperature  of  150°  C.  (302°  F.),  solid  meconic  acid, 
parting  with  its  M-ater  of  crystallization,  is  resolved  into  carbonic 
acid  gas  and  a  new  dibasic  acid,  named  comenic ;  thus:  H3C7H07  = 
HaCcHoO^  +  CO,.  At  a  somewhat  higher  temperature,  comenic 
acid  in  its  turn  is  resolved  into  caibonic  acid  gas  and  pyromeconio 
acid,  which  is  monobasic:  ^^C,Y{.f),=  l{.Q^\{ff^^CO^.  Both 
these  new  acids,  like  the  meconic,  strike  a  deep  blood-red  color  with 
'sohitions  of  ferric  salts.  The  conversion  of  meconic  into  comenic 
acid  is  also  effected  by  boiling  an  aqueous  solution,  of  the  acid,  the 
change  being  much  f\icilitated  by  the  presence  of  a  free  mineral  acid. 
When  boiled  with  an  aqueous  solution  of  either  of  the  fixed  caustic 
alkalies,  meconic  acid  is  resolved  into  carbonic  and  oxalic  acids  and 
a  dark  coloring  matter. 

In  the  following  examination  of  the  tests  for  meconic  acid  when 
in  solution,  pure  aqueous  solutions  of  the  free  acid  were  employed, 
it  being  dissolved,  when  necessary,  by  the  aid  of  a  very  gentle  heat. 
The  fractions  indicate  the  amount  of  crystallized  acid  present  in  one 
grain  of  the  fluid.  Unless  otherwise  indicated,  the  results  refer  to 
the  behavior  of  one  grain  of  the  solution. 


1.  Ferric  Cliloride. 

Solutions  of  ferric  chloride  and  of  ferric  sulphate  strike  with 
solutions  of  meconic  acid,  as  well  as  with  the  acid  and  its  salts  in 
the  solid  state,  a  deep  blood-red  color,  which  is  not  discharged  by 
either  corrosive  sublimate  or  chloride  of  gold,  but  readily  disappears 
upon  the  addition  of  a  solution  of  stannous  chlorkle.    The  red  colora- 

32 


498  -MECONIC   ACID. 

tion  manifests  itself  in  the  presence  of  even  large  excess  of  either  of 
the  free  mineral  acids. 

1.  y-J-Q-  grain  of  meconic  acid,  in  one  grain  of  water,  yields  with  a 

drop  of  the  reagent  a  deep  reddish-brown  coloration,  which  re- 
quires several  drops  of  either  of  the  concentrated  mineral  acids 
for  its  discharge,  but  it  is  unaffected,  further  than  by  dilution, 
by  several  drops  of  a  strong  solution  of  either  corrosive  subli- 
mate or  chloride  of  gold. 

2.  x^oT  E^^^^  yields  a  very  good  red  coloration. 

3.  Yo^.^o"  E^^^^^ '  ^^®  mixture  acquires  a  very  distinct  purplish-red 

color. 

4.  2-0, Too"  gr^in  yields  a  just  perceptible  red  tint.     In  several  drops 

of  this  solution,  the  red  coloration  is  quite  distinct. 
If  the  meconic  acid  solution  be  evaporated  by  a  very  gentle  heat 
to  dryness,  and  a  drop  of  the  reagent  applied  to  the  residue : 

1.  Yo","o^"o  gi'^™  •  the  deposit  assumes  a  deep  blood-red  color. 

2.  -g-Q.-ooT  g^'^ii"'  yields  a  very  distinct  red  coloration. 

3.  T-g-.^-o-o"  grails  •  the  residue  acquires  a  just  perceptible  red  hue. 
This  is  the  most  characteristic  test  yet  known  for  the  identifi- 
cation of  very  minute  quantities  of  meconic  acid,  yet  it  is  open  to 
some  few  fallacies ;  but  these  may  be  readily  guarded  against.    They 
are  as  follows : 

a.  The  alkali  sulphocyanides  and  free  sulphooyanic  acid  yield 
withferric  salts  a  red  coloration  not  to  be  distinguished  in  appearance 
from  that  occasioned  by  meconic  acid.  This  color,  however,  unlike 
that  from  meconic  acid,  is  quickly  discharged  by  a  solution  of  corro- 
sive sublimate.  This  latter  reagent,  therefore,  serves  to  distinguish 
readily  between  these  substances.  It  is  frequently  stated  that  the 
red  color  produced  by  a  sulphocyanide  is  readily  discharged  by  a 
solution  of  chloride  of  gold ;  but  this  is  not  the  case. 

Another  method  of  distinguishing  between  the  red  colors  pro- 
duced by  these  different  substances,  as  first  proposed  by  Dr.  Percy, 
is  to  place  in  the  colored  mixture  a  piece  of  pure  zinc,  and  then 
add  a  drop  of  sulphuric  acid,  when  in  the  case  of  meconic  acid  the 
color  is  slowly  discharged  with  the  evolution  of  pure  hydrogen  gas; 
whereas  the  color  of  a  sulphocyanide  is  destroyed  with  the  evolu- 
tion of  sulphuretted  hydrogen  gas,  which  may  be  recognized  by  its 
peculiar  odor,  and  by  its  blackening  a  piece  of  paper  moistened  with 
a  solution  of  lead  acetate  and  suspended  over  the  mixture.     This 


LEAD    ACETATE   TEST.  41^9 

nu'tlunl  is  not  as  simple  as  tin;  jjircc-ding;  moreover,  if  the  zinc 
should  contain  sulj)hnr,  as  is  frequently  the  case,  the  mixture  will 
evolve  sulphuretted  hydrogen,  even  in  the  absence  of  a  sulpho- 
cyanide. 

Human  saliva  has  not  unfrequently  the  property  of  striking  a 
red  color  with  ferric  salts,  due  to  the  presence  of  a  sulphocyanide ; 
and  Dr.  Pereira  states  {Mat.  Med.,  ii.  1033)  that  he  has  on  several 
occasions  obtained  the  same  results  from  the  liquid  contents  of  the 
stomach  of  subjects  in  the  dissecting-room.  However,  in  the  prep- 
aration of  the  contents  of  this  organ  for  the  detection  of  meconic 
acid,  as  pointed  out  hereafter,  any  sulphocyanide  present  would  be 
separated  with  the  foreign  matter,  when  this  objection  would  no 
lono-er  hold.  If  in  anv  case  there  is  anv  doubt  as  to  the  true  nature 
of  the  red  coloration,  this,  of  course,  may  be  removed  by  the  appli- 
cation of  a  solution  of  corrosive  sublimate. 

6.  Strono;  solutions  of  acetic  acid  and  of  its  neutral  salts  yield 
with  the  iron  reagent  a  more  or  less  red  coloration,  which,  like  that 
from  meconic  acid,  is  unaffected  by  corrosive  sublimate  and  chloride 
of  gold.  This  color  is  more  readily  affected  by  free  mineral  acids 
than  that  from  the  opium  compound.  Solutions  of  acetic  acid  and 
of  its  salts  differ  from  those  of  meconic  acid,  in  that  they  fail  to 
yield  a  precipitate  with  lead  acetate. 

e.  Ferric  salts  also  strike  with  a  concentrated  decoction  of  white 
mustard,  due  to  the  presence  of  sulphocyanide  of  siuapine,  a  red  color, 
which,  however,  is  immediately  discharged  by  corrosive  sublimate, 
but  not  by  chloride  of  gold. 

Besides  the  substances  now  mentioned,  a  strong  infusion  of  Ice- 
land moss,  and  of  some  few  other  rare  substances,  as  first  pointed 
out  by  Dr.  Pereira,  will  also  yield  a  more  or  less  red  coloration  with 
the  iron  reagent;  but  these  substances  are  uncrystallizable,  and,  like 
those  before  mentioned,  would  be  removed  from  the  liquid  during 
its  preparation  for  the  application  of  the  test  for  meconic  acid.  The 
color  produced  from  Iceland  moss  has  a  purplish  hue,  and  is  un- 
affected by  corrosive  sublimate,  but  it  is  immediately  destroyed  by 

chloride  of  gold. 

2.  Lead  Acetate. 

This  reagent  throws  down  from  solutions  of  free  meconic  acid 
and  of  its  soluble  salts  a  yellowish  or  yellowish- white,  amorphous 
precipitate  of  meconate  of  lead,  Pb32C7H07,Aq,  which  is  insoluWe 


500  MECONIC   ACID. 

in  large  excess  of  acetic  acid,  but  readily  soluble,  to  a  clear  solution, 
in  diluted  nitric  acid.  If  the  precipitate  be  treated  with  a  drop  of 
ferric  chloride  solution,  the  mixture  acquires  a  red  color. 

1.  y^  grain  of  meconic  acid,  in  one  grain  of  water,  yields  a  very 

copious,  yellowish  deposit. 

2.  j-sVo  grain  :  a  copious,  yellowish-white  precipitate. 

3.  Ynhrw  gr^'°  yields  a  very  distinct  deposit. 

4.  -gij-.Vro"  gi'^i^i  •  after  a  few  minutes  a  quite  distinct  opalescence 

appears,  and  then  little  whitish  flakes. 

Acetate  of  lead  also  produces  precipitates  with  many  other  sub- 
stances, but  in  these  cases  the  deposit  has  always,  unless  foreign 
matter  be  present,  a  pure  white  color.  Among  these  substances  may 
be  mentioned : 

a.  Sulplwcyanides,  which  yield  a  white  precipitate  which,  like 
that  from  meconic  acid,  is  reddened  by  ferric  salts;  but  it  is  readily 
soluble  in  acetiG  acid,  and  when  from  strong  solutions,  insoluble  in 
diluted  nitric  acid  ;  when  from  dilute  solutions,  however,  it  is  readily 
soluble  in  the  latter  acid  to  a  clear  solution.  When  treated  with 
metallic  zinc  and  sulphuric  acid,  sulphocyanide  of  lead  undergoes 
decomposition  with  the  evolution  of  sulphuretted  hydrogen  ;  whereas 
the  meconate  of  lead,  as  already  stated,  yields  pure  hydrogen  gas. 
6.  C/i/orme  yields  with  the  reagent  a  white  precipitate,  which  when 
from  sodium  chloride  is  readily  soluble  in  excess  of  the  precipitant, 
and  in  acetic  and  nitric  acids;  but  when  due  to  free  chlorine,  it  is 
only  sparingly  soluble  in  these  acids,  c.  Sidphuric  acid,  either  free 
or  combined,  yields  a  precipitate  which  is  iusoluble  in  acetic  acid, 
and  only  sparingly  soluble  in  nitric  acid.  d.  Soluble  carbonates 
occasion  a  precipitate  that  is  readily  soluble  with  effervescence  in 
acetic  acid.  e.  Phosphates  and  oxalates,  also,  yield  precipitates  which 
are  insoluble  in  acetic  acid,  but  readily  soluble  in  nitric  acid.  So, 
also,  the  reagent  produces  white  precipitates  with  various  organic 
])rinciples  ;  but  these  deposits  are  readily  distinguished  from  the 
meconic  acid  compound,  in  not  being  reddened  by  persalts  of  iron. 

3.  Barium  Oiloride. 

Strong  aqueous  solutions  of  meconic  acid  and  of  its  alkali  salts 
yield  with  barium  chloride  a  white  crystalline  ])recipitute  of  barium 
meconate,  which  is  insoluble  in  acetic  and  diluted  nitric  acids,  and  also 
in  caustic  ammonia. 


HYDROCHLORIC    ACID   TEST.  601 

1.  ^J.^  jrraiii  of  mecoiiic  acid:   in  a  few  iiiomenLs  crystals  begin  to 

ajjpcar,  and  in  a  very  little  time  there  is  a  quite  copious,  crys- 
talline deposit,  of  the  peculiar  fornis  illustrated  in  Plate  VII., 
fig.  4.  If  on  the  addition  of  the  reagent  the  mixture  bestirred, 
it  immediately  yields  a  copious  crystalline  deposit. 

2.  ^^-^  (Train  :  after  a  little  time,  especially  if  the  mixture  be  stirred, 

there  is  a  quite  satisfactory  deposit,  consisting  principally  of  little 
masses  of  aggregated  granules. 

3.  1^,^  (Train  :  after  sometime  the  mixture  yields  small,  microscopic 
granules. 

Although  this  reagent  also  produces  white  precipitates  in  solutions 
containing  sulphuric,  phosphoric,  and  several  other  acids,  yet  the 
crystalline  form  of  the  meconic  acid  deposit  is  peculiar. 

4.  Hydrochloric  Acid. 

This  acid,  in  its  free  state,  produces  in  aqueous  solutions  of 
meconic  acid  and  of  its  soluble  salts,  when  not  too  dilute,  a  white 
precipitate  of  free  meconic  acid,  due  to  the  insolubility  of  the  latter 
in  the  presence  of  a  limited  quantity  of  the  mineral  'acid.  This 
precipitate  is  in  the  form  of  transparent  crystalline  plates,  which,  for 
the  most  part,  are  arranged  in  beautiful  groups,  and  many  of  which, 
when  examined  by  transmitted  light  under  tiie  microscope,  appear 
beautifully  colored.  The  formation  of  the  precipitate  is  much  facili- 
tated by  stirring  the  mixture  with  a  glass  rod. 

1.  _i.^  grain  of  meconic  acid,  in  one  grain  of  water,  when  treated 

with  a  drop  of  concentrated  hydrochloric  acid:  almost  imme- 
diately crystals  begin  to  form,  and  in  a  little  time  there  is  a 
quite  copious  deposit,  Plate  VII.,  fig.  5. 

2.  -g^  grain :  after  some  minutes,  providing  very  large  excess  of 

hydrochloric  acid  be  not  employed,  the  mixture  throws  down  a 

very  satisfactory,  crystalline  precipitate. 
Hydrochloric  acid  also  produces  white  precipitates  in  solutions 
containing  silver,  lead,  antimony,  and  mercurous  combinations. 
But  the  silver,  mercury,  and  antimony  deposits  are  amorphous,  and 
that  from  lead  is  in  the  form  of  crystalline  needles;  whereas  the 
meconic  acid  precipitate,  even  from  complex  organic  mixtures,  is 
always  in  the  form  of  crystalline  plates.  It  need  hardly  be  remarked 
that  the  meconic  acid  precipitate  also  differs  from  these  fallacious 
substances  in  striking  a  red  color  with  persalts  of  iron. 


502  MECONIC    ACID. 

5.  Silver  Nitrate. 

This  reagent  produces  in  aqueous  solutions  of  the  organic  acid 
an  amorphous  precipitate  of  silver  meconate,  which  is  readily  soluble 
in  ammonia  and  in  nitric  acid,  but  insoluble  in  acetic  acid.  The 
color  of  this  precipitate  depends  somewhat  upon  the  relative  quantity 
of  reagent  employed  :  when  the  latter  is  in  excess,  the  deposit  has  a 
yellow  color;  whilst  if  there  is  excess  of  meconic  acid  present,  the 
precipitate  is  white.  The  yellow  precipitate  consists  of  the  tribasic 
meconate  of  silver,  AggCyHO^;  while  the  white  is  a  dibasic  salt  of 
the  metal,  AggHC^HO^. 

1.  YST  grain  of  meconic  acid,  in  one  grain  of  water,  yields  a  very 

copious,  pale  yellow  or  yellowish-white,  gelatinous  precipitate, 
which  after  a  time  acquires  a  pure  yellow  color.  If  several 
drops  of  the  solution  be  precipitated  by  excess  of  the  reagent, 
the  deposit  has  at  once  a  rather  bright  yellow  hue. 

2.  ytq-q  grain  :   a  good,  flocculent  precipitate,  having   only  a  just 

perceptible  yellow  tint. 

3.  Yo'.Wo  grain :  after  a  time  a  quite  distinct  flaky  deposit. 

Silver  nitrate  also  produces  yellow  or  yellowish-white  precipi- 
tates in  solutions  containing  phosphoric,  arsenious,  and  silicic  acids; 
but  neither  of  these  acids  strikes  a  red  color  with  persalts  of  iron. 

6.  Potassium  Ferrocyanide. 

Strong  aqueous  solutions  of  meconic  acid  and  of  its  alkali  salts, 
when  treated  with  this  reagent,  yield,  especially  if  the  mixture  be 
stirred  and  allowed  to  stand,  a  crystalline  precipitate,  which  is  only 
slowly  soluble  in  acetic  acid. 

One  grain  of  a  1-lOOth  solution  of  the  free  acid  yields  after  a 
little  time  large  groups  of  hair-like  crystals,  Plate  VII.,  fig.  6 ; 
after  about  half  an  hour  the  mixture  becomes  converted  into  an 
almost  solid  crystalline  mass.  Solutions  but  little  more  dilute  than 
this  altogether  fail  to  yield  a  precipitate.  The  crystals  produced  by 
this  reagent  are  quite  characteristic. 

7.   Calcium  Chloride. 
This  reagent    produces  in  concentrated    solutions  of  the  alkali 
meconates  a  white,  or  yellowish-white  precipitate  of  meconate  of  cal- 
cium.    One  grain  of  a  1-lOOth  solution  of  the  free  acid  vields  no 


MECX)NIC   ACID    AND    MORPHINE,  503 

immediate  precipitate,  but  after  a  little  time  large  groups  of  colorless 
tnmsj)arent  crystals  separate  from  the  mixture,  Plate  VIII.,  fig.  1. 
The  precipitate  is  insoluble  in  large  excess  of  acetic  acid;  its  forma- 
tion is  much  facilitated  by  agitating  the  mixture. 

OlJter  Rccufcnts. — Copper  sulphale  solution  throws  duwn  from 
strong  aqueous  solutions  of  meconic  acid  a  greenish-blue,  amorphous 
precipitate  of  meconate  of  copper,  which  is  soluble  in  acetic  acid  and 
in  ammonia.  Ammonio-copper  sulphate  fails  to  produce  a  precipi- 
tate, even  in  concentrated  solutions  of  the  free  acid. 

Saturated  aqueous  solutions  of  the  free  acid  fail  to  yield  a  pre- 
cipitate with  either  of  the  following  reagents:  auric  chloride,  potas- 
sium ferrocyanide,  picric  acid,  platinic  chloride,  corrosive  sublimate, 
iodine  in  potassium  iodide,  bromine  in  bromohydric  acid,  tannic  acid, 
and  potassium  ohromate. 

Separation  of  Meconic  Acid  and  Morphine  from  Solutions 
OF  Opium  and  Complex  Organic  Mixtures. 

The  presence  of  opium  may  be  established,  as  already  stated,  by 
showing  the  presence  of  meconic  acid  and  morphine.  In  fact,  this 
may  be  done  by  simply  proving  the  presence  of  meconic  acid;  yet, 
when  possible,  it  is  always  advisable  to  prove  also  the  presence  of 
morphine.  Should  there  be  a  failure  to  detect  either  of  these  sub- 
stances, it  is  pretty  certain  that  there  would  also  be  a  failure  to  dis- 
cover any  of  the  other  principles  peculiar  to  the  drug.  This  arises 
from  the  fact  that  the  methods  at  present  known  for  the  separation  of 
these  latter  substances  from  complex  organic  mixtures  are  much  less 
delicate  than  those  for  the  recovery  at  least  of  meconic  acid.  In 
their  pure  state,  however,  some  of  these  principles  may  be  identified 
in  even  smaller  quantity  than  the  organic  acid.  Before  proceed- 
ing to  the  preparation  of  a  suspected  mixture  for  the  application 
of  chemical  tests,  it  should  be  carefully  examined  for  the  odoi^  of 
opium ;  this,  however,  may  not  be  recognized  even  when  the  drug  is 
present  in  quite  notable  quantity. 

Suspected  Solutions  and  Contents  of  the  Stomach. — If 
the  liquid  presented  for  examination  appears  to  be  a  simple  aqueous 
solution  of  opium  or  laudanum,  as  is  sometimes  the  case,  it  is  slightly 
acidulated  with  acetic  acid,  and  evaporated  at  a  low  temperature,  on 


504  MECONIC  ACID   AND   MOEPHINE. 

a  water-bath,  to  a  small  volume,  then  filtered,  and  the  filtrate  ex- 
amined in  the  manner  hereafter  directed.  When,  however,  the  sus- 
pected mixture  is  of  a  complex  nature  and  contains  organic  solids, 
these  are  cut  into  very  small  pieces,  the  mass,  if  not  already  suffi- 
ciently liquid,  treated  with  pure  water  and  a  little  alcohol,  and  the 
whole  distinctly  acidulated  with  acetic  acid.  It  is  then  very  moder- 
ately heated,  with  frequent  stirring,  for  half  an  hour  or  longer,  al- 
lowed to  cool,  the  liquid  strained  through  muslin,  and  the  solid 
residue  on  the  strainer  well  washed  with  strong  alcohol  and  strongly 
pressed,  the  washings  being  collected  with  the  first  liquid.  The 
united  liquids  are  now  concentrated  to  a  very  small  volume,  on  a 
water-bath  at  a  temperature  not  exceeding  71°  C.  (160°  F.),  and 
then,  after  cooling  and  dilution  with  water  if  necessary,  filtered 
through  paper  previously  moistened  with  water.  Any  solid  matter 
thus  separated  is  washed  with  a  little  diluted  alcohol,  and  the  wash- 
ings added  to  the  first  filtrate.  If  during  the  concentration  of  the 
liquid  much  solid  matter  separates,  it  should  be  removed  by  a  muslin 
strainer. 

The  clear  filtrate  thus  obtained  is  treated  with  slight  excess  of 
lead  acetate,  by  which  any  meconic  acid  present  will  be  precipitated 
as  meconate  of  lead,  together  with  more  or  less  foreign  matter ;  at 
the  same  time,  any  morphine  and  other  opium  principles  present  * 
will  remain  in  solution.  Should  the  liquid  contain  a  sulphocyanide, 
this  will  also  remain  in  solution,  since,  as  already  pointed  out,  these 
salts  are  not  precipitated  in  the  presence  of  free  acetic  acid  by  the 
lead  reagent.  When  the  precipitate  has  completely  subsided,  the 
mixture  is  transferred  in  small  portions  to  a  small  moistened  filter, 
and  the  solid  residue  left  on  the  filter  washed  with  a  little  pure  water, 
this  being  collected  with  the  first  filtrate.  The  analysis  now  divides 
itself  into  two  branches  : 

1st.  Contents  of  the  filter. — While  the  filter  is  still  moist,  its  lower 
end  is  pierced  with  a  glass  rod,  and  the  contents  carefully  washed  by 
a  jet  of  water  from  a  wash-bottle  into  a  tall  test-tube,  and  the  pre- 
cipitate allowed  completely  to  subside.  After,  if  thought  best,  de- 
canting a  portion  of  the  clear  supernatant  liquid,  the  precipitate  is 
diffused  in  the  remaining  fluid  and  treated  with  a  stream  of  sulphu- 
retted hydrogen  gas,  as  long  as  a  precipitate  is  produced.  By  this 
treatment  any  meconate  of  lead  present  will  be  decomposed,  the 
metal  being  thrown  down  as  black  sulphide,  while  the  liberated 


SEPARATION  FROM  ORGANIC  MIXTURES. 


505 


meconic  acid  will  ontcv  into  solution.  The  liquid  is  then  filtered,  and 
the  filtrate  concentrated  at  a  moderate  temperature  on  a  water-hath, 
when  the  excess  of  suli)hurctted  hydrogen  present  will  be  dissipated. 
If  the  liquid  contains  a  quite  notable  quantity  of  meconic  acid,  it 
will  now  usually  have  a  more  or  less  reddish  or  brownish  color. 

After  the  solution  thus  obtained  has  cooled,  a  drop  of  it  is 
removed  to  a  watch-glass  and  tested  with  a  ferric  salt ;  if  this  indi- 
cates the  presence  of  meconic  acid  in  quite  notable  quantity,  the 
remaining  liquid  is  examined  by  some  of  the  other  tests  for  the 
organic  acid.  Should,  however,  the  iron-test  fliil  to  yield  positive 
results  or  indicate  the  presence  of  the  acid  in  only  minute  quantity, 
the  remaining  fluid  is  carefully  concentrated  to  a  very  small  volume, 
and  consecutive  drops  examined  by  ferric  chloride,  hydrochloric  acid, 
and  barium  chloride  or  potassium  ferricyanide.  Should,  in  any  ease, 
the  iron-test  fail,  it  is  quite  certain  that  the  other  tests  mentioned 
would  also  fail,  since  the  former  is  much  the  more  delicate  in  its 
reactions.  If  the  concentrated  liquid  contains  much  foreign  matter, 
this  may  verv  much  interfere  with  the  normal  reactions  of  the  tests. 
Under  these  circumstances,  the  liquid  may  be  evaporated  at  a  very 
gentle  temperature  to  dryness,  the  residue  extracted  with  a  small 
quantity  of  strong  alcohol,  the  filtered  alcoholic  extract  evaporated 
to  dryness,  and  the  residue  thus  obtained  dissolved  in  a  very  small 
quantity  of  warm  water  and  the  solution  then  tested.  In  some  in- 
stances, however,  it  will  be  found  best,  for  the  separation  of  foreign 
matter,  to  reprecipitate  the  meconic  acid  by  lead  acetate,  and  then 
treat  the  precipitate  in  the  manner  above  described. 

By  the  method  now  described,  the  1-1 00th  of  a  grain  of  meconic 
acid  in  solution  in  twenty-five  grains  of  water  may  be  precipitated 
and  recovered  without  any  appreciable  loss.  So,  also,  an  alcoholic 
solution  of  one  grain  of  opium  mixed  with  foreign  organic  matter, 
when  treated  after  this  method  and  the  final  solution  reduced  to  four 
drops,  gave  with  the  four  reagents  before  named  results  somewhat 
better  in  each  case  than  a  1-lOOth  solution  of  the  pure  acid,  the 
last  three  reagents  producing  copious  crystalline  precipitates  of  the 
forms  peculiar  to  the  organic  acid. 

When  a  solution  has  been  prepared  in  this  manner,  the  fallacies 
attending  the  iron-test  under  certain  conditions  do  not  apply.  The 
manner  in  which  any  sulphocyanide  present  would  be  avoided  has 
already  been  indicated  ;  and,  as  the  acetates  are  all  soluble,  they 


506  MECONIC   ACID    AND    MORPHINE. 

also  would  remain  in  solution  in  the  filtrate ;  nor  could  any  of  the 
organic  infusions  that  strike  a  red  color  with  the  iron  reagent  remain 
on  the  filter  with  the  washed  meconate  of  lead. 

Another  method  frequently  advised  for  decomposing  the  mec- 
onate of  lead  for  the  recovery  of  the  organic  acid,  is  to  digest  it  at  a 
moderate  heat  with  diluted  sulphuric  acid,  under  the  action  of  which 
it  is  resolved  into  insoluble  lead  sulphate  and  free  meconic  acid, 
which  enters  into  solution.  Since,  however,  as  already  pointed  out, 
meconic  acid  is  prone  to  undergo  decomposition  in  the  presence  of 
a  free  mineral  acid,  especially  if  the  mixture  be  heated  to  near  the 
boiling  temperature,  this  method  may  be  attended  with  considerable 
loss ;  moreover,  the  presence  of  sulphuric  acid  would  interfere  with 
some  of  the  tests  for  the  organic  acid. 

2d.  The  filtrate. — The  above  filtrate — which  contains  the  mor- 
phine in  the  form  of  acetate,  and  some  of  the  other  opium  principles, 
together  with  any  excess  of  lead  acetate  employed  in  the  precipi- 
tation of  the  meconic  acid — is  treated  with  excess  of  sulphuretted 
hydrogen  gas,  for  the  purpose  of  precipitating  the  lead.  When  the 
precipitate  has  completely  deposited,  which  may  be  facilitated  by 
the  application  of  a  very  gentle  heat,  the  liquid  is  filtered,  and  the 
filtrate  evaporated  on  a  water-bath  to  dryness ;  the  residue  thus  ob- 
tained is  well  stirred  with  a  little  pure  water,  and  the  solution  again 
filtered.  A  drop  of  the  solution  may  now  be  tested  for  morphine 
by  nitric  acid,  and  another  by  ferric  chloride.  Whether  these  tests 
indicate  the  presence  of  the  alkaloid  or  not,  the  remaining  liquid, 
after  dilution  if  necessary,  is  rendered  slightly  alkaline  by  a  strong 
solution  of  sodium  carbonate,  allowed  to  stand  some  little  time,  and 
then  agitated  with  a  few  volumes  of  absolute  ether.  This  liquid  will 
extract  some  of  the  opium  principles  and  more  or  less  coloring  mat- 
ter, but  leave  the  liberated  morphine  in  the  alkaline  aqueous  fluid. 
After  carefully  decanting  the  ethereal  liquid,  and  placing  it  aside 
for  future  examination  if  necessary,  the  alkaline  liquid  may  be 
examined  by  either  of  the  following  methods. 

a.  Alcoholic- ether. — The  liquid  is  violently  agitated  for  some 
minutes  with  from  four  to  five  times  its  volume  of  a  mixture  con- 
sisting of  two  parts  of  absolute  ether  and  one  part  of  pure  alcohol,  by 
which  the  alkaloid  will  be  extracted  from  the  aqueous  fluid.  This 
operation  is  best  performed  by  placing  the  alkaline  liquid  in  a  long 
graduated  tube,  and  then  adding  sufiicient  of  the  prepared  ethereal 


SEPARATION    FROM    ORGANIC    MIXTURES.  507 

mixture  so  tliat  after  agitation  and  repose  tlie  volume  of  the  former 
liquiil  is  sli<;htly  diminished.  In  certain  proj)ortions  the  liquids 
will  form  a  liomoirtMU'ous  mixture,  \vhil(!  in  others  the  volume  of  the 
aqueous  fluid  will  be  augmented,  and  in  others  still  it  will  he  dimin- 
ished. If  any  dilHeulty  is  experienced  in  regard  to  the  .reparation 
of  the  liquids,  a  little  pure  ether  should  he  added. 

The  alcoholic-ether  is  now  carefully  decanted  into  a  watch-glass 
or  capsule,  and  allowed  to  evaporate  spontaneously,  when  the  mor- 
phine will  usually  be  left  in  its  crystalline  form;  when,  however, 
there  is  only  a  minute  quantity  of  the  alkaloid  present  or  it  is  mixed 
with  much  foreign  matter,  it  may  remain  in  its  amorphous  state. 
When  the  residue  has  become  quite  dry,  it  is  carefully  washed,  by 
gently  rotating  a  few  drops  of  pure  water  over  it  in  the  glass  and 
then  decanting  the  liquid.  Small  portions  of  the  residue  are  now 
separately  examined  by  nitric  acid,  sulpho-raolybdic  acid,  and  the 
iron-tests,  and  anv  ren)aining  portion  dissolved,  by  the  aid  of  a  trace 
of  acetic  acid,  in  a  very  small  quantity  of  water,  and  the  solution 
then  submitted  to  some  of  the  liquid  tests  for  morphine.  By  ex- 
posing a  portion  of  the  aqueous  solution  to  the  vapor  of  ammonia 
until  it  acquires  a  very  slightly  alkaline  reaction,  and  then  exposing 
it  to  the  air  for  several  hours  if  necessary,  the  alkaloid  may  be  de- 
posited in  its  crystalline  form,  even  when  present  in  only  very  minute 
quantity.  In  this  manner  we  have  on  several  occasions  obtained 
very  satisfactory  crystals,  when  every  other  method  failed  to  reveal 
the  alkaloid  in  this  form. 

On  applying  the  method  now  described,  for  the  extraction  of 
morphine,  to  a  complex  organic  mixture  containing  only  one  grain 
of  opium,  the  raeconic  acid  having  been  previously  precipitated  from 
the  aqueous  solution  by  lead  acetate,  the  alcoholic-ether  left  on  spon- 
taneous evaporation  a  very  fine  crystalline  deposit  of  the  alkaloid. 

b.  Amyl  alcohol. — Another  method  for  the  extraction  of  the 
morphine,  is  to  agitate  the  alkaline  liquid,  as  first  suggested  by  Uslar 
and  Erdmann  (see  ante,  424),  with  two  or  three  times  its  volume  of 
hot  amyl  alcohol,  in  which,  as  already  shown,  the  alkaloid  is  rather 
freely  soluble.  When  the  fluids  have  completely  separated,  the 
upper,  or  alcoholic,  liquid  is  transferred,  by  means  of  a  caoutchouc 
pipette,  to  a  watch-glass ;  the  aqueous  fluid  is  then  washed  with  a 
fresh  portion  of  the  hot  alcohol,  and  this  transferred  to  the  watch- 
glass  containing  the  liquid   first  employed.      In  the  absence  of  a 


508  MECONIC  ACID   AND   MORPHINE. 

caoutchouc  pipette,  the  alkaline  liquid  may  be  removed  from  the 
alcoholic  by  closing  the  upper  end  of  an  ordinary  pipette  with  the 
finger  and  passing  the  open  end  to  the  bottom  of  the  fluid  mixture, 
when,  upon  removing  the  finger,  the  aqueous  liquid  will  be  forced 
into  the  tube,  and  may  thus  be  removed.  The  employment  of  the 
ordinary  suction-pipette,  on  account  of  the  injurious  action  of  the 
alcohol  on  the  respiratory  organs,  is  inadmissible. 

The  amyl  alcohol  is  now  evaporated,  at  a  very  gentle  heat  on  a 
water-bath,  to  dryness,  when  the  alkaloid  may  be  left  in  its  crystalline 
form ;  but  it  is  much  less  apt  to  be  left  in  this  form,  under  these 
circumstances,  than  when  separated  by  spontaneous  evaporation  from 
the  above  ethereal  mixture.  Should  the  residue  be  amorphous,  it 
may  be  redissolved  in  a  small  quantity  of  diluted,  ordinary  alcohol, 
and  the  liquid  allowed  to  evaporate  spontaneously.  The  residue  is 
then  examined  in  the  ordinary  manner. 

In  the  application  of  this  method  for  the  recovery  of  minute 
quantities  of  morphine  from  complex  mixtures  containing  known 
quantities  of  opium,  we  have  obtained  very  satisfactory  results;  and 
on  the  whole,  perhaps,  this  process  is  preferable  to  the  ether  method 
before  described. 

c.  Acetic  ether. — A  third  method  that  may  be  employed  for  the 
extraction  of  the  alkaloid  from  the  foregoing  alkaline  solution,  is  by 
means  of  acetic  ether,  as  advised  by  M.  Alfred  Valser.  (Chem.  News, 
1864,  ix.  289  ;  from  Jour,  de  Pharm.  et  Chimie,  xliii.  49,  63.)  The 
operation  may  be  conducted  in  much  the  same  manner  as  when 
amyl  alcohol  is  employed,  and  the  liquid  allowed  to  evaporate 
spontaneously.  If  this  method  be  adopted,  it  should  be  borne  in 
mind  that  morphine  is  much  less  soluble  in  pure  acetic  ether  than  in 
either  amyl  alcohol  or  a  mixture  of  alcohol  and  ether;  and,  there- 
fore, that  a  correspondingly  larger  proportion  of  this  liquid  will  be 
required  for  the  extraction  of  a  given  quantity  of  the  alkaloid.  On 
the  other  hand,  this  liquid,  when  pure,  has  a  much  less  solvent 
action  upon  foreign  organic  matter  than  either  of  the  other  liquids 
named,  particularly  a  mixture  of  alcohol  and  ether  ;  at  the  same 
time  it  is  more  likely  than  amyl  alcohol,  on  evaporation,  to  leave 
the  alkaloid  in  the  crystalline  form.  It  may  here  be  remarked  that 
acetic  ether,  as  found  in  the  shops,  not  unfrequently  contains  so 
much  alcohol  as  to  cause  it  to  mix  in  all  proportions  with  water, 
when  agitated  with  this  liquid. 


SEPARATION  FROM  ORGANIC  MIXTURES. 


509 


The  absolute  ether  with  whicli  the  alkaline  solution  was  washed, 
previous  to  the  extraction  of  the  ni()r|)hiiie,  eontains  narcotine  and 
some  other  opium  principles,  together  with  more  or  less  foreign 
organic  matter.  ^Vhen  evaporated  spontaneously,  it  usually  leaves, 
if  "there  is  not  much  foreign  matter  i)rescnt,  a  transi)arent  amorphous 
residue,  which  when  treated  with  a  drop  of  concentrated  sulphuric 
acid  dissolves  to  a  blood-red  solution  ;  if  a  small  crystal  of  potassium 
nitrate  be  stirred  in  this  mixture,  the  color  of  the  latter  is  changed 
to  brownish  or  purplish.  These  results,  however,  being  due  to  the 
combined  action  of  several  different  substances,  are  subject  to  consid- 
erable variation. 

Porphi/roxin.—For  the  detection  of  small  quantities  of  opium, 
Merck  advises  to  take  advantage  of  the  property  possessed  by  por- 
phyroxin,  one  of  the  constituents  of  the  drug,  of  being  reddened 
when  heated  with  hydrochloric  acid.  For  this  purpose  the  opium 
solution  is  rendered  alkaline  by  potassium  hydrate,  and  agitated  with 
pure  ether,  in  which  this  principle  is  soluble.  A  strip  of  white 
bibulous  paper  is  then  repeatedly  dipped  into  the  decanted  ethereal 
liquid,  the  paper  being  dried  between  each  immersion  ;  the  paper  is 
now  moistened  with  hydrochloric  acid,  and  exposed  to  the  vapor  of 
boiling  water,  when  it  will  acquire,  especially  after  dr.ying,  a  more  or 
less  rose-red  color.  On  following  these  directions  for  the  examina- 
tion of  solutions  containing  very  notable  quantities  of  opium,  we 
failed  to  obtain  very  satisflictory  results;  with  larger  quantities  of  the 
drug,  however,  the  red  coloration  was  well  marked. 

According  to  Merck,  porpJiyroxin,  in  its  pure  state,  may  be  ob- 
tained by  the  following  process.  Powdered  opium  is  exhausted  by 
boiling  ether,  then  made  into  a  pulp  with  water,  slight  excess  of 
potassium  carbonate  added,  the  mixture  agitated  with  ether,  the 
ethereal  liquid  evaporated  to  dryness,  the  residue  thus  obtained  dis- 
solved in  a  small  quantity  of  very  dilute  hydrochloric  acid,  and  the 
solution  rendered  slightly  alkaline  by  ammonia,  by  which  the  por- 
phyroxin,  together  with  pa'-amorphine,  will  be  precipitated.  On 
dissolving  the  precipitate  in  ether,  and  allowing  the  liquid  to  evapo- 
rate spontaneously,  the  former  of  these  principles  is  left  in  the  form 
of  a  resin,  while  the  latter  is  deposited  in  the  crystalline  form.  They 
may  now  be  separated  by  cautiously  treating  the  mixture  with  alco- 
hol, in  which  the  porphyroxin  is  soluble;  the  alcoholic  solution  is 
then  evaporated  to  dryness  at  a  low  temperature.      Porphyroxin 


510  MECONIC   ACID   AND   MORPHINE. 

is  described  as  a  neutral  substance,  which  crystallizes  in  brilliant 
needles,  is  readily  soluble  in  alcohol  and  in  ether,  but  insoluble  in 
water.  It  is  but  proper  to  add  that  the  existence  of  this  substance, 
as  a  distinct  opium  principle,  has  been  doubted  by  several  experi- 
mentalists. According  to  O.  Hesse,  it  consists  of  a  mixture  of 
several  distinct  principles. 

Examination  for  Morphine  alone. — When  there  is  reason  to  sus- 
pect that  morphine,  or  one  or  other  of  its  salts,  is  present  in  its  free 
state,  the  same  method  of  analysis  may  be  followed  as  for  its  recovery 
from  organic  solutions  containing  opium,  except  that  the  use  of  lead 
acetate  is  omitted.  Thus,  the  mixture,  slightly  acidulated  with  acetic 
acid,  is  digested  at  a  moderate  temperature-  with  diluted  alcohol, 
allowed  to  cool,  the  liquid  strained,  then  concentrated  on  a  water- 
bath  to  a  small  volume,  filtered,  and  the  filtrate  evaporated  to  dry- 
ness. The  residue,  thus  obtained,  is  treated  with  a  small  quantity  of 
water,  the  solution  filtered,  the  filtrate  rendered  slightly  alkaline  with 
sodium  carbonate,  washed  with  absolute  ether,  and  the  alkaloid,  if 
present,  extracted  by  either  of  the  methods  heretofore  described. 

It  rarely  happens,  under  these  circumstances,  that  the  analyst  is 
able  to  determine  the  acid  with  which  the  morphine  was  combined. 
Should,  however,  the  mixture  be  not  too  complex,  it  may  be  con- 
centrated on  a  water-bath  to  a  very  small  volume,  then  gently 
warmed  with  a  little  concentrated  alcohol,  and  the  filtered  liquid 
allowed  to  evaporate  spontaneously,  when  the  morphine  salt  may  be 
deposited  in  its  crystalline  state.  A  portion  of  any  deposit  of  the 
salt  thus  obtained  is  dissolved  in  a  small  quantity  of  pure  water, 
and  the  nature  of  the  acid  determined  by  appropriate  tests. 

From  the  Tissues. — Thus  far,  with  few  exceptions,  there  seems 
to  have  been  an  entire  failure  to  recover  the  poison  from  the  tissues, 
in  poisoning  by  opium,  and  its  active  alkaloid.  And  in  the  exami- 
nation of  the  liver  of  two  diflFerent  animals  poisoned  by  the  drug, 
we  met  with  similar  results.  If  it  be  desired  to  examine  the  tissues 
for  the  absorbed  poison,  the  solid  organ,  as  a  portion  of  the  liver, 
cut  into  very  small  pieces  and  triturated  in  a  mortar,  is  made  into  a 
thin  paste  with  water  containing  a  little  alcohol,  then  acidulated  with 
acetic  or  sulphuric  acid,  and  the  whole  digested,  with  frequent  stir- 
ring, at  a  moderate  heat  for  about  an  hour.  When  the  mass  has 
cooled,  the  liquid  is  strained  through  muslin,  and  the  solids  upon 
the  strainer  well  washed  with  diluted  alcohol  and  strongly  pressed. 


RECOVERY    FROM    TIIF,    BI^OOD.  511 

The  mixed  liquids  may  tlien  ho  examined  after  the  manner  already 
described. 

From  the  Blood. — Among  various  methods  pursued  for  the 
recovery  of  minute  quantities  of  meconic  acid  and  morphine,  when 
purposely  added  to  healtiiy  blood,  the  following  gave  the  best  results. 
The  fluid,  acidulated  with  acetic  acid  in  the  proportion  of  about 
eight  drops  of  the  concentrated  acid  for  each  fluid-ounce  of  blood, 
is  thoroughly  agitated,  best  in  a  tolerably  wide-mouthed  bottle,  with 
an  equal  volume  of  strong  alcohol,  and  the  mixture  gently  heated  in 
a  porcelain  dish  on  a  water-bath,  until  the  albuminous  matter  has 
collected  into  little  flakes.  The  cooled  mass  is  thrown  on  a  wet  linen 
strainer,  and  the  solids  well  washed  with  alcohol  and  strongly  pressed. 
These  are  again  thoroughly  mixed  with  fresh  alcohol,  gently  warmed, 
and  the  liquid  strained  as  before.  The  united  strained  liquids  are 
now  concentrated  on  a  water-bath  to  a  small  volume,  again  strained, 
and  then  filtered.  If  during  the  concentration  of  the  liquid  much  solid 
matter  separates,  as  is  usually  the  case,  it  is  removed  by  a  strainer. 

The  filtered  liquid  thus  obtained  is  evaporated  to  dryness  on  a 
water-bath,  the  residue  digested  with  a  small  quantity  of  nearly  ab- 
solute alcohol,  the  solution  filtered,  and  the  filtrate  evaporated  to  dry- 
ness. This  residue  is  gently  warmed  with  a  small  qi>antity  of  water, 
and  the  liquid  filtered.  On  now  treating  the  filtrate  with  lead  acetate, 
any  meconic  acid  present  will  be  precipitated  as  meconate  of  lead  :  it 
should  be  borne  in  mind  that  under  these  circumstances  the  lead  re- 
agent not  unfrequently  produces  a  yellowish-white  precipitate,  even 
in  the  absence  of  meconic  acid.  Any  precipitate  thus  obtained  is 
separated  by  a  filter  and  examined  in  the  usual  manner  for  the  or- 
ganic acid,  while  the  filtrate  is  tested  for  morphine. 

The  repeated  digestions  with  alcohol,  in  the  above  process,  are 
rendered  necessary  on  account  of  the  extreme  tenacity  with  which 
these  opium  principles,  especially  the  meconic  acid,  adhere  to  the  al- 
buminous matter  of  the  blood.  In  fact,  this  organic  acid  forms  with 
albumen  a  precipitate,  which  is  very  sparingly  soluble  in  water,  and 
only  slowly  yields  the  acid  to  alcohol. 

In  operating  on  a  fluid-ounce  of  blood,  according  to  this  method, 
the  smallest  quantities  of  meconic  acid  and  morphine  from  which  we 
succeeded  in  recovering  crystals  of  both  substances  were  the  one- 
twentieth  of  a  grain  of  each.  In  one  of  these  instances,  the  final  mor- 
phine solution  being  concentrated  to  three  drops,  two  of  the  drops 


512  MECONIC  ACID   AND   MORPHINE. 

gave  respectively  witli  nitric  acid  and  ferric  chloride  very  satisfac- 
tory evidence  of  the  presence  of  the  alkaloid,  while  the  third,  when 
exposed  to  the  vapor  of  ammonia,  and  then  to  the  air  for  several 
hours,  deposited  four  comparatively  large  groups  of  crystals  of  the 
pure  alkaloid.  In  the  same  case,  the  evidence  of  the  presence  of  the 
meconic  acid  was  about  equally  satisfactory. 

With  mixtures  containing  smaller  quantities  of  the  opium  prin- 
ciples, the  final  solutions,  even  when  only  the  1-lOOth  of  a  grain  of 
each  substance  had  been  added,  gave  results  that  no  doubt  were 
due  to  the  presence  of  these  principles ;  yet  the  reactions  were  by  no 
means  conclusive.  On  examining  for  only  one  of  these  substances, 
crystals  may  be  obtained  from  a  somewhat  smaller  quantity  of  either 
than  before  stated. 

On  applying  the  foregoing  method  to  the  examination  of  the 
blood  of  eight  different  dogs  and  cats  poisoned  by  opium,  the  final 
solutions  in  some  instances  gave  results  which  there  is  little  doubt 
were  due  to  the  presence  of  meconic  acid  and  morphine;  while  in 
others  they  failed  to  reveal  the  presence  of  a  trace  of  either  of  these 
substances.  In  no  instance,  however,  were  crystals  obtained  or  were 
the  results,  with  perhaps  a  single  exception,  such  as  would  have  been 
satisfactory  in  an  unknown  case. 

In  the  exception  just  mentioned,  two  grains  of  morphine  in  solu- 
tion had  been  given  to  a  large  cat;  an  hour  afterward  an  ounce  of 
laudanum  was  administered,  and  in  another  hour  one  ounce  more. 
In  an  hour  after  the  last  dose  the  animal  was  killed  by  a  blow  on  the 
head,  and  four  ounces  of  blood  were  carefully  taken  from  the  body. 
On  treating  the  whole  of  the  fluid  after  the  manner  before  described, 
and  concentrating  the  final  solution,  supposed  to  contain  meconic 
acid,  to  two  drops,  and  testing  one  of  these  directly  with  ferric 
chloride,  and  evaporating  the  other  to  dryness  and  testing  the  resi- 
due in  the  same  manner,  both  gave  results  identical  with  those  occa- 
sioned by  minute  traces  of  the  organic  acid.  So,  also,  the  morphine 
solution,  when  reduced  to  two  drops  and  these  tested  separately  by 
nitric  acid  and  a  ferric  salt,  gave  equally  distinct  evidence  of  the 
presence  of  the  alkaloid. 

Bearing  in  mind  that  at  most  only  a  minute  quantity  of  the 
organic  poisons  enters  the  blood,  and  the  great  loss  attending  the 
separation  of  the  opium  ])rincii)les  from  this  fluid,  we  were  not  much 
disappointed  in  the  results  of  the  foregoing  experiments. 


FAIUTIIK   TO    DETKCr.  513 

The  Urine. — Accordino;  to  M.  liouohardat,  morphine,  when 
taken  either  in  its  free  state  or  under  the  form  of  opium,  si)eediiy 
appears  in  the  urine,  and  may  be  detected  by  the  liquid  yielding 
a  reddish-brown  precipitate  with  a  solution  of  iodine  in  potassium 
iodide.  Since,  however,  as  we  have  already  seen,  this  reagent  also 
produces  similar  precipitates  with  most  of  the  other  alkaloids  and 
with  certain  other  organic  substances,  this  reaction  in  itself  could 
by  no  means  be  regarded  as  direct  proof  of  the  presence  of  this  alka- 
loid. Moreover,  we  find  that  the  reagent  not  unfrequently  throws 
down  a  precipitate  from  what  may  be  regarded  as  normal  urine; 
while,  on  the  other  hand,  it  sometimes  fails  to  produce  a  precipitate, 
even  when  comparatively  large  quantities  of  the  alkaloid  have  been 
purposely  added  to  this  liquid. 

Failure  to  detect  the  Poison. — It  has  not  unfrequently 
happened  that  there  was  a  failure  to  detect  a  trace  of  either  meconic 
acid  or  morphine  in  any  part  of  the  alimentary  canal,  even  when 
large  quantities  of  the  poison  had  been  taken  and  the  conditions  for 
its  detection  were  apparently  very  favorable.  Thus,  in  a  case  re- 
lated by  Dr.  Christison,  he  failed  to  obtain  any  direct  evidence  of 
the  presence  of  the  poison  in  the  contents  of  the  stomach  of  a  young 
woman  who  died  in  five  hours  after  taking  not  less  than  two  ounces 
of  laudanum.  In  another  case,  the  contents  of  the  stomach,  evac- 
uated two  hours  after  seven  drachms  of  laudanum  were  swallowed, 
had  no  odor  of  opium,  nor  did  they  reveal  the  presence  even  of 
meconic  acid. 

Prof.  L.  A.  Buchner  relates  an  instance  in  which  he  failed  to 
find  any  morphine  in  the  stomach  of  a  boy,  five  years  old,  who  was 
killed  by  three  doses,  of  two  grains  each,  of  the  acetate  of  morphine. 
{Amer.  Jour.  Pharm.,  Sept.  1867,  415.)  And  Dr.  Ebertz  reports  a 
case  {Ann.  d'Hyg.,  1875,  220)  in  which  a  woman  took  in  mistake  for 
quinine  about  four  grains  (.25  gramme)  of  the  hydrochloride,  and 
died  from  its  effects  in  from  forty  to  fifty  minutes.  On  examination 
of  the  contents  of  the  stomach,  the  upper  portion  of  the  small  intes- 
tines, the  liver,  spleen,  kidneys,  and  the  blood  of  the  right  ventricle, 
no  trace  of  morphine  was  found.  So,  also.  Dr.  Ogston  mentions  a 
case  {Med.  Jur.,  1878,  567)  in  which  a  woman  had  taken  not  less 
than  from  nine  to  ten  grains  of  the  hydrochloride,  and  died  within 
a  few  hours,  and,  although  there  had  been  no  vomiting  and  no  remedy 
applied,  a  most  careful  examination  by  himself  and  the  late  Prof. 

33 


514  MECONIC  ACID   AND   MOEPHINE. 

Gregory  failed  to  detect  any  trace  of  morphine  in  the  alimentary 
tube  or  elsewhere. 

Since  the  tests  and  methods  for  separating  meconic  acid  from 
foreign  substances  are  somewhat  more  satisfactory  than  those  for 
morphine,  in  poisoning  by  opium,  the  acid  has  sometimes  been  de- 
tected when  there  was  a  failure  to  detect  the  alkaloid. 

On  the  other  hand,  the  poison  has  been  detected  even  when 
taken  in  only  comparatively  small  quantity  and  death  was  delayed 
for  several  hours.  In  a  case  related  by  Dr.  Skae,  in  which  not  more 
than  half  an  ounce  of  laudanum  had  been  taken,  and  death  did  not 
occur  until  thirteen  hours  afterward,  the  contents  of  the  stomach 
furnished  evident  indications  of  the  presence-  of  morphine,  and  faint 
evidence  of  meconic  acid.  It  need  hardly  be  remarked  that,  since 
opium  or  its  active  alkaloid  is  so  frequently  administered  medici- 
nally, the  detection  of  mere  traces  of  the  poison  in  the  dead  body 
would  not  in  itself  be  positive  proof  that  it  was  the  cause  of  death. 

Quantitative  Analysis. — For  the  purpose  of  estimating  the 
quantity  of  morphine  present  in  an  aqueous  solution  of  any  of  its 
salts,  the  somewhat  concentrated  solution  may  be  slightly  supersatu- 
rated with  pure  aqua  ammonise,  and  allowed  to  stand  quietly  in  a 
cool  place  for  about  twenty-four  hours.  The  alkaloid,  with  the  ex- 
ception of  the  merest  trace,  will  now  be  precipitated  in  its  crystalline 
form.  The  crystals  are  then  carefully  separated  from  the  liquid, 
washed  with  absolute  ether,  dried  at  the  ordinary  temperature,  and 
weighed.  One  hundred  parts  by  weight  of  the  pure  crystallized 
alkaloid  represent  123.8  parts  of  crystallized  hydrochloride  of  mor- 
phine, Ci7Hi9N03,HCl,3Aq ;  125  parts  of  the  crystallized  sulphate, 
2C„Hi9N03:  H2S04,5Aq;or  131.6  parts  of  the  acetate  of  morphine, 
C,,H,9N03,C2HA,3Aq. 

The  quantity  of  opium  or  morphine  found  in  the  stomach,  in 
poisoning  by  one  or  other  of  these  substances,  is  usually  too  minute 
to  admit  of  a  direct  quantitative  analysis.  Under  these  circum- 
stances, the  quantity  may  sometimes  be  estimated  with  considerable 
accuracy  by  observing  the  intensities  of  the  reactions  of  the  reagents 
applied,  and  comparing  these  with  the  reactions  of  known  quantities 
of  the  poison. 


NARCOTINE.  515 


IV.  Narcotine. 


History. — The  existence  of  narcotine  was  iirst  pointed  out,  in 
1803,  by  Derosne;  but  Robiquet,  in  1817,  was  the  first  to  indicate 
its  chomical  nature.  Blyth,  in  1844,  assigned  to  it  the  fornnula 
C23II05NO7.  The  more  recent  investigations  of  Messrs.  Matthiessen 
and  Foster  led  them  to  adopt  the  formula  C22H23NO7.  {Jour.  Chem. 
Soc,  1863,  342.)  Wertheim  has  described  three  homologous  forms 
of  narcotine  in  opium,  having  the  formulae  022^23^^7?  ^^23ll25^^7> 
and  C.^HgyNOy,  which  he  named,  respectively,  methylo-,  ethylo-,  and 
propvlo-narcotine,  from  the  fact  that  when  passed  over  soda-lime 
they  yield  methylamine,  ethylamiue,  and  propylamine.  The  investi- 
gations of  Matthiessen  and  Foster,  as  well  as  those  of  Dr.  Anderson, 
however,  render  the  existence  of  these  varieties  very  doubtful. 

Narcotine  usually  constitutes  from  six  to  eight  per  cent,  of  good 
Smyrna  opium  ;  but  in  some  varieties  of  the  drug  it  forms  only  about 
one  per  cent.  As  this  substance  may  be  extracted  from  the  drug  by 
ether,  without  the  addition  of  either  an  alkali  or  an  acid,  it  would 
appear  that  it  exists  principally  in  its  free  state.  It  has  only  feebly 
basic  properties. 

Preparation. — This  substance  may  be  obtained  either  by  adding 
ammonia  to  the  mother-liquor  from  which  hydrochloride  of  morphine 
has  been  prepared,  or  by  digesting  the  insoluble  part  of  opium  in 
acetic  acid,  and  precipitating  by  ammonia.  The  impure  narcotine  is 
purified  by  digesting  its  hot  alcoholic  solution  with  animal  charcoal 
and  recrystallizing  (Gregory). 

Physiological  Effects. — Much  discrepancy  has  existed  among  ex- 
perimentalists in  regard  to  the  action  of  narcotine  upon  the  animal 
system,  some  observers  considering  it  as  almost  inert,  whilst  others 
attribute  to  it  narcotic  properties.  These  narcotic  eflPects,  however, 
may  have  been  due  to  the  presence  of  morphine  in  the  preparation 
employed.  Dr.  O'Shaughnessy,  of  Calcutta,  attributed  to  it  powerful 
antiperiodic  properties,  and  used  it,  he  states,  with  great  success  in 
the  treatment  of  intermittent  fever.  He  prescribed  it  in  doses  of 
three  grains,  three  times  a  day. 

Dr.  S.  Weir  Mitchell,  in  experiments  upon  himself,  found  narco- 
tine to  produce  little  or  no  effect,  even  when  taken  in  doses  of  thirty 
grains.     It  seemed  to  be  equally  inert  when  given  by  the  mouth  to 


516  NARCOTINE. 

pigeons ;  but  when  administered  hypodermically  in  two-grain  doses, 
it  caused  feebleness,  unsteady  gait,  and  early  convulsions,  without  in 
any  instance  stupor.  [Amer.  Jour.  Med.  Sei.,  Jan.  1870,  23.)  This 
observer  also  found  that  pigeons  possessed  an  entire  immunity  to 
the  action  of  opium  and  morphine,  even  when  administered  in  enor- 
mous doses. 

Chemical  Peoperties. — In  its  pure  state,  narcotine  crystallizes 
in  the  form  of  transparent,  colorless,  rhombic  prisms ;  sometimes,  how- 
ever, it  appears  in  the  form  of  oblong  plates,  and  at  other  times  as 
a  granular  powder.  In  its  solid  state,  it  is  nearly  destitute  of  taste, 
but  when  in  solution,  it  has  an  intensely  bitter  taste,  even  exceeding 
that  of  morphine.  When  moderately  heated,  it  fuses  to  a  colorless 
liquid  ;  at  higher  temperatures  it  takes  fire,  burning  with  a  smoky 
flame.  According  to  Prof.  Guy,  narcotine  fuses  at  115.5°  C.  (240°  F.), 
and  volatilizes  at  154.4°  C.  (310°  F.). 

Under  the  action  of  oxidizing  agents  narcotine  is  readily  decom- 
posed, giving  rise  to  a  variety  of  new  compounds,  among  which  is 
opianyl,  one  of  the  other  opium  principles.  The  pure  alkaloid,  when 
in  solution,  has  little  or  no  action  upon  reddened  litmus-paper,  in 
which  respect  it  differs  from  morphine ;  so  also,  unlike  morphine,  it 
fails  to  strike  a  blue  color  either  with  a  ferric  salt  or  with  a  mixture 
of  iodic  acid  and  starch. 

Narcotine  fails  to  neutralize  diluted  acids,  but  it  readily  unites 
with  them,  forming  salts,  which,  for  the  most  part,  are  uncrystal- 
lizable.  Concentrated  sulphu7nG  acid  slowly  dissolves  the  alkaloid 
to  a  yellow  solution,  which,  when  stirred  with  a  crystal  of  j)otassium 
nitrate,  acquires  a  deep  blood-red  color.  When  the  simple  acid  so- 
lution is  moderately  heated,  it  acquires  a  purplish  color,  even  when 
only  a  very  minute  quantity  of  the  alkaloid  is  present.  When  the 
acid  solution  is  stirred  with  a  crystal  of  potassium  dichromate,  the 
results  depend  much  upon  the  relative  quantity  of  the  salt  employed 
(see  post).  Concentrated  nitrie  acid  also  dissolves  the  alkaloid  to  a 
more  or  less  yellow  solution  ;  hydrochloric  acid  dissolves  it  without 
change  of  color.  It  is  slowly  soluble  in  large  excess  of  concentrated 
acetic  acid,  but  insoluble  in  the  diluted  acid. 

When  large  excess  of  powdered  narcotine  is  digested  for  twenty- 
four  hours,  at  the  ordinary  temperature,  with  pure  water,  this  liquid 
fails  to  dissolve  even  the  1— 20,000th  of  its  weight  of  the  alkaloid. 
Absolute  ether,  under  similar  circumstances,  takes  up  one  part  of 


BEHAVIOi:    WITH     11  IK    ALKALIES.  617 

the  alkaloid  in  20.S  luirts  of  the  liquid,  iSarcoliiio  is  Holuhle  in  all 
proportions  in  chloroform,  and  dissolves  readily  in  alcohol,  but  is 
insoluble  in  the  caustic  alkalies.  The  salts  of  the  alkaloid  are,  for 
the  most  part,  readily  soluble  in  water  and  in  alcohol. 

Narcotine  and  morphine  may  be  separated  from  each  other  by 
agitating  the  mixture  with  chloroform  or  ether,  which  will  dissolve 
the  former  but  not  the  latter ;  so,  also,  these  substances  may  be  sepa- 
rated bv  a  solution  of  either  of  the  fixed  caustic  alkalies  or  by  diluted 
acetic  acid,  which  will  take  up  the  morphine  but  not  the  narcotine. 

Narcotine  may  be  readily  separated  from  aqueous  solutions  of  its 
salts  by  treating  the  solution  with  slight  excess  of  a  free  alkali,  and 
agitating  the  mixture  with  chloroform  or  ether.  Upon  spontaneous 
evaporation,  the  extracting  liquid  will  usually  leave  the  alkaloid  in 
the  form  of  beautiful  groups  of  brilliant  crystals,  similar  to  those  of 
the  crystallized  acetate  (Plate  VIII.,  fig.  3). 

In  the  following  examination  of  the  reactions  of  narcotine  when 
in  solution,  the  pure  alkaloid  was  dissolved  in  water  by  the  aid  of  the 
least  possible  quantity  of  hydrochloric  acid.  The  fractions  employed 
indicate  the  amount  of  pure  alkaloid  in  solution  in  one  grain  of 
water;  and,  unless  otherwise  intimated,  the  results  refer  to  the  be- 
havior of  one  grain  of  the  solution. 

1.   The  Alkalies  and  their  Carbonates. 

The  fixed  caustic  alkalies,  and  ammonia,  as  also  their  carbonates, 
produce  in  aqueous  solutions  of  salts  of  narcotine  a  white  precipitate 
of  the  free  alkaloid,  which  is  insoluble  in  even  large  excess  of  the 
precipitant  and  in  diluted  acetic  acid,  but  readily  soluble  in  hydro- 
chloric and  nitric  acids.  After  a  little  time  the  precipitate  becomes 
crystalline. 

1.  YTo  gi'E^i"    of  narcotine,  in  one   grain    of  water,  yields  a  very 

copious,  amorphous  deposit,  and  very  soon  the  mixture  becomes 
a  nearly  solid  crystalline  mass. 

2.  Yruu  grain  yields  an  immediate  precipitate,  which  in  a  little  time 

becomes  converted  into  beautiful,  and  somewhat  characteristic, 
crystalline  tufts,  Plate  YIII.,  fig.  2. 

3.  Yo'.TOir  grain :    an  immediate  cloudiness,  and  in  a  few  moments 

crystals  appear;  after  a  little  time  there  is  a  quite  good  crystal- 
line precipitate,  the  crystals  having  the  forms  just  illustrated. 

4.  4-(5-,^-c-(r  gi'ain :  if  only  a  very  minute  trace  of  the  reagent  be  em- 


618  NAECOTINE. 

ployed,  the  mixture  soon  becomes  opalescent,  and  after  a  little 
time,  especially  when   examined  by  the  microscope,  yields  a 
very  satisfactory  deposit  of  crystalline  needles.     This  precipi- 
tate fails  to  appear  in  the  presence  of  even  very  slight  excess 
of  the  reagent. 
If  a  drop  of  an  aqueous  solution  of  a  salt  of  narcotine  be  ex- 
posed to  the  vapor  of  ammonia,  it  soon  becomes  covered  with  a 
white  crystalline  film,  even  when  it  contains  only  the  l-5000th  of 
its  weight  of  the  alkaloid. 

2.  Sulphuric  Acid  and  Potassium  Nitrate. 

If  a  solution  of  narcotine  or  of  any  of  its  salts  be  evaporated  to 
dryness,  the  residue  dissolved  in  a  small  quantity  of  concentrated 
sulphuric  acid,  and  then  a  small  crystal  of  potassium  nitrate  or  a 
trace  of  free  nitric  acid  be  stirred  in  the  mixture,  the  latter  quickly 
acquires  a  deep  blood-red  color,  even  if  only  a  minute  quantity  of 
the  alkaloid  be  present.  This  color  is  discharged  by  large  excess  of 
free  nitric  acid. 

1.  Y0T  g^^iii  of  narcotine,  when  dissolved  in  a  single  drop  of  the 

concentrated  acid,  and  a  small  crystal  of  nitre  added,  yields  a 
deep  red  coloration.  If  the  nitre  be  first  dissolved  in  the  acid 
and  the  mixture  then  allowed  to  flow  over  the  narcotine  deposit, 
the  latter  immediately  assumes  a  deep  red  color,  and  slowly 
dissolves  to  a  solution  of  the  same  hue. 

2.  YWo"  gr^i^^  '•  if  the  acid  mixture  be  flowed  over  the  deposit,  the 

latter  becomes  blood-red,  and  soon  dissolves  to  a  yellow  solution. 

3.  Yo".Wo   gi'^ij^  •  the  deposit  acquires  a  red  color,  and  very  soon 

dissolves  to  a  faintly  yellow  solution. 

This  is  one  of  the  most  characteristic  tests  yet  known  for  the 
detection  of  narcotine.  Under  its  action  the  true  nature  of  the 
precipitate  produced  by  the  caustic  alkalies  or  their  carbonates  may 
be  fully  established.  For  this  purpose  the  precipitate  is  washed, 
dried,  then  dissolved  in  a  drop  of  sulphuric  acid,  and  a  small  crystal 
of  nitre  stirred  in  the  solution. 

When  a  solution  of  narcotine  in  concentrated  sulphuric  acid  is 
stirred  with  a  very  small  crystal  of  potassium  dichromate,  the  fluid 
acquires  a  beautiful  wine  color,  which  remains  unchanged  for  many 
days.  If,  however,  an  excess  of  the  potassium  salt  be  used,  the 
liquid  passes  through  several  colors,  and  ultimately  becomes  either 


POTASSIUM    ACETATE   TEST. 


519 


green  or  blue,  tlie  liiuvl  color  depending  upon  the  relative  amount 
of  the  salt  employed.  The  permanent  color  is  readily  obtained  by 
stirrinj^  the  potassium  salt  in  the  acid  solution  until  it  imparts  the 
desired  tint,  and  then  removing  the  crystal  from  the  mixture.  The 
color  may  thus  be  obtained  from  even  a  very  minute  quantity  of  the 

alkaloid. 

3.  Potassium  Acetate. 

A  solution  of  potassium  acetate  produces  in  aqueous  solutions 

of  salts  of  narcotine  a  white  precipitate  of  the  acetate  of  narcotine, 

which  is  insoluble  in   large  excess  of  the  precipitant,  but  readily 

soluble  in  most  free  acids,  and  in  excess  of  the  narcotine  solution. 

If,  therefore,  the  solution  contain  a  free  acid,  or  if  the  reagent  be 

not  added  in  excess,  the  mixture  may  fail  to  yield  a  precipitate. 

The   formation   of  the  precipitate   from   dilute   solutions  is  much 

facilitated  by  stirring  the  mixture. 

1.  __L_  grain  of  narcotine,  in  one  grain  of  water,  yields  a  very  copious, 

amorphous  deposit,  which  after  a  time  becomes  converted  into 
beautiful  groups  of  crystals,  Plate  YIII.,  fig.  3. 

2.  —l^  grain  :  an   immediate  cloudiness,  and  soon  a  quite  good 

crystalline  deposit. 

3.  ^i_  grain  yields  after  a  little  time  a  good  deposit  of  crystalline 

needles. 

4.  ^-^1^5-5-  grain  :  after  a  few  minutes  crystals  appear. 

5.  ^\^^  grain:  after  several    minutes  crystalline  needles  appear 

along  the  edge  of  the  drop,  and  after  a  time  there  is  a  very 
satisfactory  deposit. 

The  same  precipitate  is  thrown  dow^n  from  solutions  of  salts  of 
narcotine  by  other  acetates,  such  as  the  acetate  of  barium,  of  zinc, 
and  of  lead  ;  but  the  reactions  of  these,  especially  the  last-mentioned, 
are  not  quite  so  delicate  as  that  of  the  potassium  salt. 

The  production  of  a  precipitate  by  the  neutral  alkali  acetates 
is  rather  characteristic  of  narcotine,  since  it  is  the  only  substance, 
except  solutions  of  salts  of  silver  and  mercurous  compounds,  with 
which  they  produce  a  precipitate,  at  least  in  the  form  of  an  acetate. 
In  solutions  containing  silver  or  mercury,  however,  the  reagent  fails 
to  produce  a  precipitate  unless  the  solution  be  quite  concentrated  and 
a  corresponding  solution  of  the  reagent  be  employed. 

As  the  acetates  thus  serve  for  the  detection  of  narcotine,  so,  on 
the  other  hand,  solutions  of  salts  of  the  alkaloid  serve  for  the  pre- 


620  NAECOTINE. 

cipitation  of  combined  acetic  acid,  for  which  heretofore  we  had  no 
ready  precipitant.  However,  as  the  acetate  of  narcotine  is  readily 
soluble  in  excess  of  a  soluble  salt  of  the  alkaloid,  the  latter  is  not  so 
delicate  a  test  for  the  acetates  as  these  are  for  narcotine. 

4.  Potassium  Chr ornate. 

This  reagent  throws  down  from  aqueous  solutions  of  salts  of  narco- 
tine a  yellow,  amorphous  precipitate,  which  after  a  time  becomes  crys- 
talline.   The  precipitate  is  readily  soluble  in  acids,  even  acetic  acid. 

1.  Y^  grain  of  narcotine,  in  one  grain  of  water,  yields  a  very  copious 

deposit,  which  slowly  assumes  the  crystalline  form. 

2.  xru'o"  grain :  a  quite  good  precipitate,  which  soon  yields  crystal- 

line tufts  of  the  same  form  as  produced  by  the  caustic  alkalies 
(Plate  VIII.,  fig.  2). 

3.  5-^5-0  grain  :  much  the  same  as  2.    The  formation  of  the  crystals 

is  much  facilitated  by  stirring  the  mixture. 

4.  Yo.Vro  E^^^^'^  yields  in  a  very  little  time,  especially  by  stirring,  a 

good  crystalline  deposit. 

5.  ■25-,Vfo  grahi :  after  a  few  minutes  a  very  satisfactory  deposit  of 

crystalline  needles  and  tufts. 

The  forms  of  the  crystals  produced  by  this  reagent  are  somewhat 
peculiar  to  solutions  of  narcotine. 

Potassium  dichromate  produces  in  somewhat  strong  solutions  of 
salts  of  the  alkaloid  a  yellow,  amorphous  precipitate,  which  after 
a  time  becomes  granular.  One  grain  of  a  1-1 00th  solution  of  the 
alkaloid  yields  a  copious  deposit;  and  a  similar  quantity  of  a  1— 500th 
solution  a  quite  fair,  light  yellow  precipitate;  but  a  1-lOOOth  solu- 
tion fails  to  yield  any  visible  change. 

5.  Potassium  Sulphocyanide. 

This  reagent  occasions  in  solutions  of  salts  of  narcotine  a  white 
precipitate,  which  is  insoluble  in  the  alkalies,  but  readily  soluble  in 
acids,  even  acetic  acid. 

1.  Y^  grain  of  narcotine  yields  a  very  copious  deposit,  which  soon 

becomes  a  mass  of  crystals  of  the  same  form  as  those  produced 
by  the  caustic  alkalies. 

2.  y-^g-g-  grain  :  an  immediate  precipitate,  which  soon  becomes  crys- 

talline. 


BROMINE    IN    BROMOIIYDRIC    ACID    TEST.  521 

3.  -j-y;^  grain:    after  a  little  time,  especially  if   the  mixture   be 

stirred  with  a  gla&s  rod,  it  yields  a  very  satisfactory  crystalline 

deposit. 

4,  -^-^  grain:  after  a  time  a  (luite  satisfactory  deposit  of  crystal- 

line needles. 
This   reagent   produces  no   precipitate  in   solutions  of  salts  of 

morphine. 

6.  Auric  Chloi'ide. 

Trichloride  of  gold  produces  in  solutions  of  salts  of  narcotine  a 
bright  yellow,  amorphous  precipitate,  the  color  of  which  is  per- 
manent, even  upon  the  addition  of  caustic  potash:  in  this  respect 
narcotine  differs  from  morphine.  Upon  heating  the  mixture  the 
precipitate  dissolves,  but  it  is  reproduced  as  the  solution  cools.  The 
precipitate  is  but  very  sparingly  soluble  in  large  excess  of  acetic  acid. 

1.  _^  grain    of  narcotine,  in  one  grain    of   \\-ater,  yields  a  very 

copious  precipitate. 

2.  ^-^  grain :   a  very  good  deposit,  which  is  insoluble  in  several 

drops  of  a  strong  solution  of  potassium  hydrate. 

3.  j-g-Ljj-y  grain  yields  a  very  satisfactory  precipitate. 

4.  ^-—^  grain  :  after  a  little  time  a  quite  perceptible  deposit. 

5.  ^y^j^  grain  yields  a  perceptible  turbidity. 

7.  Iodine  in  Potassium  Iodide. 
A  solution    of  iodine  in   potassium   iodide  throws  down   from 
solutions  of  salts  of  narcotine  a  reddish-brown,  amorphous  precipi- 
tate, which  is  nearly  insoluble  in  the  caustic  alkalies,  and  only  very 
sparingly  soluble  in  acetic  acid. 

1.  _i_j.  grain  of  narcotine  yields  a  very  copious  deposit. 

2.  Ywro  g^^'"  •  ^  copious  precipitate. 

3.  -^-L^  grain   yields  a  quite  good    precipitate,  which  is  readily 

soluble  to  a  clear  solution  in  potassium  hydrate. 

4.  -g-g-i-g^  grain  :  a  brownish-yellow  deposit. 

5.  ^-,5-j5-ijj^5^  grain  yields  a  very  perceptible  turbidity. 

8.  Bromine  in  Bromohydric  Acid. 
A  solution  of  bromohydric  acid  saturated  with  bromine  produces 
in  solutions  of  salts  of  narcotine  a  bright  yellow,  amorphous  precipi- 
tate, which  is  insoluble  in  large  excess  of  the  precipitant,  and  only 
sparingly  soluble  in  acetic  acid.     Upon  the  addition  of  potassium 


622  NAECOTINE. 

hydrate,  the  precipitate  acquires  a  white  color,  except  when  produced 
from  very  dilute  solutions,  when  it  dissolves  to  a  clear  liquid. 

1.  Ywo  gJ'S'iii  of  narcotine  yields  a  very  copious  precipitate,  which 

after  a  time  dissolves,  but  it  is  reproduced  upon  further  addition 
of  the  reagent. 

2.  iQ-QQ  grain :  a  copious  precipitate,  which  is  soluble  in  potassium 

hydrate,  but  is  almost  immediately  replaced  by  a  white  deposit. 

3.  xo.^-o-o  grain :    a  quite  good  deposit,  which,  when  dissolved  in 

potassium  hydrate,  yields  a  slight,  white  precipitate. 

4.  -g-Q-.Too"  grain  yields  a  quite  distinct,  yellowish  precipitate. 

5.  i-Q  o'iWo'  gJ^ain  :  a  quite  distinct  cloudiness. 

9.  Potassium  Ferrocyanide. 

This  reagent  produces  in  aqueous  solutions  of  salts  of  narcotine 
a  dirty- white,  amorphous  precipitate,  which  is  very  readily  soluble 
in  acetic  acid,  but  insoluble  in  large  excess  of  the  precipitant. 

1.  Y^  grain  of  narcotine,  in    one   grain   of  water,  yields  a  quite 

copious  deposit. 

2.  YToo"  gi^ain  :  a  very  good  precipitate. 

3.  i-o,Wo  grain  yields  a  quite  strong  turbidity. 

Potassium  ferricyanide  throws  down  from  quite  strong  solutions 
of  narcotine  a  yellow,  amorphous  precipitate,  which  is  readily  soluble 
in  excess  of  the  precipitant  and  in  acetic  acid. 

10.  Picric  Acid. 

An  alcoholic  solution  of  picric  acid  throws  down  from  solutions 
of  salts  of  narcotine  a  bright  yellow,  amorphous  precipitate,  which 
is  slowly  soluble  in  large  excess  of  the  precipitant,  and  also  in  large 
excess  of  acetic  acid. 

1.  YTo  grain  of  narcotine  yields  a  very  copious  precipitate,  which 

remains  amorphous. 

2.  YoVo  grain :  a  very  good  deposit. 

3.  yo.Vfo  grain  yields  a  quite  obvious  precipitate. 

Platinie  chloride  produces  in  somewhat  strong  solutions  of  salts 
of  narcotine  a  light  yellow,  amorphous  precipitate,  which  is  sparingly 
soluble  in  acetic  acid.  One  grain  of  a  1-lOOth  solution  of  the  alka- 
loid yields  a  very  copious  precipitate,  and  the  same  quantity  of  a 
1-lOOOth  solution,  a  quite  fair  deposit;  but  a  l-2500th  solution 


CODEINE.  523 

yields  no  iiulications.  Palladium  chlojnde  produces  similar  results. 
Tannic  acid  and  corrosive  sublimate  throw  down  from  concentrated 
solutions  of  the  alkaloid  white,  amorphous  precipitates. 

When  somewhat  strong  solutions  of  salts  of  narcotine  are  treated 
with  a  stream  of  chlorine  gas,  the  liquid  quickly  assumes  a  yellow 
color,  which  soon  changes  to  reddish-brown ;  on  now  adding  a  solu- 
tion of  ammonia,  the  mixture  acquires  a  deep  brown  color.  Ten 
grains  of  a  1-1 00th  solution  of  the  alkaloid  will  yield  these  results. 
A  similar  quantity  of  a  1-lOOOth  solution,  when  treated  with  the 
gas,  acquires  a  distinct  yellow  tint,  which  is  changed  to  reddish- 
brown  by  ammonia.  In  these  reactions  narcotine  closely  resembles 
morphine. 

V.  Codeine. 

History. — Codeine,  or  codeia,  as  it  is  frequently  called,  was  first 
discovered,  in  1832,  by  M.  Robiquet.  It  exists  in  opium  in  combina- 
tion with  meconic  acid,  and  usually  forms  considerably  less  than  one 
per  cent,  of  the  crude  drug.  The  formula  for  codeine,  in  its  anhy- 
drous state,  according  to  Gerhardt,  is  CisHgiNOg;  in  its  crystalline 
form,  it  usually  contains  one  molecule  of  water  of  crystallization. 
It  has  a  bitter  taste  and  strong  alkaline  properties,  q\iickly  restoring 
the  blue  color  of  reddened  litmus-paper. 

Preparation. — Codeine  may  be  obtained,  according  to  Dr.  Greg- 
ory, by  concentrating  the  mother-liquor  from  which  morphine  has 
been  precipitated,  when,  after  a  time,  a  mixture  of  the  hydrochlo- 
rides of  codeine  and  morphine  will  be  deposited.  This  deposit  is 
dissolved  in  a  little  hot  water,  and  the  solution  treated  with  excess 
of  potassium  hydrate,  which  precipitates  the  codeine,  partly  in  the 
form  of  crystals  and  partly  as  a  viscid  mass,  which  soon  becomes 
solid  and  crystalline ;  at  the  same  time,  most  of  the  morphine  prasent 
remains  in  solution  in  the  alkaline  liquid.  The  precipitate  is  then 
treated  with  ether  or  with  water,  either  of  which  will  dissolve  the 
codeine,  while  any  morphine  present  will  remain  undissolved.  The 
ethereal  solution,  upon  spontaneous  evaporation,  leaves  the  alkaloid 
in  the  form  of  beautiful  anhydrous  prisms ;  while  the  aqueous  solu- 
tion deposits  it  in  the  form  of  octahedral  crystals,  containing  one 
molecule  of  water  of  crystallization. 

Physiological  Effects. — The  statements  in  regard  to  the  effects  of 
codeine  when  taken  into  the  stomach  have  been  quite  contradictory. 


524  CODEINE. 

According  to  the  results  of  some  observers,  it  has  strong  narcotic 
properties,  similar  to  those  of  morphine,  only  that  it  has  to  be  given 
in  larger  quantity,  and  never  induces  the  unpleasant  after-effects  so 
frequently  witnessed  in  the  administration  of  that  alkaloid.  Dr. 
Gregory  observed  that  in  some  instances  it  excited  a  sense  of  intense 
itching  of  the  entire  skin,  and  states  that  probably  the  itching  caused 
in  some  persons  by  opium  and  some  of  the  salts  of  morphine  may  be 
due  to  the  action  of  codeine,  this  substance  being  not  unfrequently 
present  in  some  of  the  preparations  of  morphine.  On  the  other 
hand,  other  observers  were  led  to  conclude  that  codeine  was  nearly 
or  entirely  destitute  of  narcotic  properties.  Five  grains  of  codeine, 
taken  by  Dr.  S.  Weir  Mitchell,  caused  slight  giddiness  and  nausea, 
with  some  cerebral  heaviness.  Dr.  Wood  states  that  he  has  given 
it  in  doses  of  eight  grains  per  day  without  any  marked  effect. 

Chemical  Peopeeties. — Codeine  is  a  white,  crystallizable,  and 
strongly  basic  substance,  precipitating  the  oxides  of  many  of  the 
metals  from  solutions  of  their  salts,  but  in  its  turn  being  precipitated 
by  the  caustic  alkalies.  It  is  readily  distinguished  from  morphine 
by  not  striking  a  blue  color  with  a  ferric  salt.  When  heated,  it  first 
parts  with  its  water  of  crystallization,  and  at  about  120°  C.  (248°  F.) 
fuses  to  a  colorless  liquid,  which  at  higher  temperatures  takes  fire, 
burning  with  the  evolution  of  dense  fumes. 

Codeine  completely  neutralizes  diluted  acids,  combining  with 
.them  to  form  salts,  most  of  which  are  readily  crystallizable.  Con- 
centrated sulphuric  acid  slowly  dissolves  the  pure  alkaloid  without 
change  of  color;  if  a  solution  of  this  kind  be  heated  on  a  water- 
bath,  it  acquires  a  beautiful  purple  color,  even  when  only  a  minute 
quantity  of  the  alkaloid  is  present :  this  result,  however,  is  some- 
v/hat  influenced  by  the  amount  of  acid  and  heat  employed.  A  small 
crystal  of  potassium  nitrate  stirred  in  the  cold  acid  solution  yields 
a  faint  greenish,  then  reddish,  coloration;  while  a  crystal  of  potas- 
sium dichroraate  yields  a  green  color,  due  to  the  formation  of  ses- 
quioxide  of  chromium.  Concentrated  nitric  acid,  it  is  said,  produces 
no  change  of  color  with  codeine ;  but  the  few  samples  we  have 
examined  became  more  or  less  orange-yellow,  and  dissolved  to  a 
yellow  solution,  when  treated  with  this  acid,  especially  when  a  not 
inconsiderable  quantity  of  the  alkaloid  was  employed.  Similar 
results  have  also  been  obtained  by  various  other  observers.  Stannous 
chloride  added  to  the  nitric  acid  solution  causes  it  to  undergo  little 


CHEMICAL   i»ropp:rtie8.  525 

or  no  change.  Ilydrocliloric  acid  readily  dissolves  the  alkaloid  to 
a  colorless  solution,  which  rcnuiins  unchanged  upon  the  applicration 
of  heat. 

When  excess  of  Hnely-powdered  codeine  is  digested  with  pure 
water  at  tiie  ordinary  temperature,  with  frequent  agitation,  for 
twenty-four  hours,  the  solution  then  filtered,  and  the  fdtrate  evap- 
orated to  dryness,  it  leaves  a  crystalline  residue  indicating  that  one 
part  of  the  alkaloid  had  dissolved  in  128  parts  of  the  fluid.  It  is 
much  more  freely  soluble  in  hot  water,  from  which,  however,  much 
of  the  excess  separates  as  the  solution  cools.  Absolute  ethei-,  under 
the  foregoing  conditions,  dissolves  one  part  of  the  alkaloid  in  55 
parts  of  the  liquid.  Chlorofoiin,  under  similar  conditions,  takes  up 
one  part  in  21.5  parts  of  fluid.  The  alkaloid  is  also  freely  soluble 
in  alcohol,  and  somewhat  soluble  in  solutions  of  the  caustic  alkalies, 
but  less  so  than  in  pure  water.  The  salts  of  codeine  are,  for  the 
most  part,  readily  soluble  in  water,  and  in  alcohol ;  but  they  are 
nearly  or  altogether  insoluble  in  ether,  and  in  chloroform. 

Aqueous  solutions  of  codeine,  when  not  too  dilute,  have  a  strongly 
alkaline  reaction  and  a  very  bitter  taste.  The  alkaloid  may  be 
extracted  from  its  aqueous  solution  by  agitation  with  ethe^' ;  but,  as 
codeine  is  not  very  much  less  soluble  in  water  than  in  ether,  repeated 
agitations  with  the  latter  are  required  for  the  complete  separation  of 
the  alkaloid.  It  is  much  more  readily  extracted  by  chloroform.  By 
either  of  these  liquids  it  may  be  separated  from  morphine.  The 
alkaloid  may,  of  course,  be  extracted  in  a  similar  manner  from 
aqueous  solutions  of  its  salts,  by  first  treating  them  wnth  slight 
excess  of  a  free  mineral  alkali. 

The  codeine  employed  in  the  following  investigations  was  pre- 
pared by  E.  iSIerck,  of  Darmstadt :  it  was  in  the  form  of  large, 
colorless  crystals,  and  apparently  perfectly  pure.  Its  solutions  were 
prepared  in  the  form  of  the  acetate.  The  fractions  indicate  the 
fractional  part  of  a  o^rain  of  the  pure  alkaloid  in  solution  in  one 
grain  of  water ;  and,  unless  otherwise  stated,  the  results  refer  to  the 
behavior  of  one  grain  of  the  solution. 

1.   The  Caustic  Alkalies. 

The  fixed  caustic  alkalies  and  ammonia  throw  down  from  con- 
centrated aqueous  solutions  of  salts  of  codeine  a  white,  amorphous 
precipitate  of  the  pure  alkaloid,  which  is  readily  soluble  in  free  acids. 


526  CODEINE. 

One  grain  of  a  1-lOOth  solution  of  the  alkaloid  yields  a  quite 
good  deposit,  which  remains  amorphous.  On  account  of  the  solu- 
bility of  codeine  in  water,  solutions  but  little  more  dilute  than  that 
just  mentioned  fail  to  yield  a  precipitate  with  either  of  these  reagents. 

Since  the  alkaloid  is  less  soluble  in  alkaline  solutions  than  in 
pure  water,  it  is  partly  precipitated  from  its  pure  aqueous  solutions, 
when  not  too  dilute,  by  the  caustic  alkalies. 

2.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  produces  in  solutions  of 
salts  of  codeine  a  reddish-brown  precipitate,  which  is  readily  soluble 
to  a  colorless  solution  in  potassium  hydrate;  it  is  also  soluble  in 
acetic  acid. 

1.  ^-1^  grain  of  codeine,  in  one  grain  of  water,  yields  a  very  copious 

precipitate,  which  after  a  time  becomes  more  or  less  crystalline, 
Plate  VIII.,  fig.  4.  The  precipitate  is  readily  soluble  in  alco- 
hol, from  which  after  a  time  it  separates  in  the  form  of  crystal- 
line plates,  Plate  VIII.,  fig.  5,  which  are  especially  beautiful 
under  polarized  light.  Solutions  but  little  more  dilute  than 
this  fail  to  yield  crystals. 

2.  YWWo  grain  yields  a  copious  deposit. 

3.  Yo^.^-QT  gi'aiii :  a  very  good,  reddish-yellow  precipitate, 

4.  -3^,^-0-0  grain :  a  yellowish  deposit. 
5/_^-g-^L__  grain  :  a  quite  perceptible  precipitate. 
6.   5-ot3oTo"  grain  yields  a  distinct  turbidity. 

This  reagent  also  produces  crystalline  precipitates  with  some  of 
the  other  opium  principles;  but  the  deposits  produced  by  the  reagent 
from  most  other  substances  remain  amorphous. 

3.  Bromine  in  Bromohydric  Aeid. 

A  solution  of  bromohydric  acid  saturated  with  bromine  throws 
down  from  solutions  of  salts  of  codeine  a  yellow,  amorphous  pre- 
cipitate, which  after  a  time  dissolves,  but  it  is  reproduced  upon 
further  addition  of  the  reagent. 

1.  -L  grain  of  codeine  yields  a  very  copious,  bright  yellow  deposit. 

2.  xoW   grain  :  a  copious  precipitate. 

3.  xo.Too"  grain ;  a  fair,  yellow  deposit. 

4.  2-5,^-0^  grain  yields  a  quite  perceptible  cloudiness. 


AURIC   OIir.ORIDE   TEST.  527 

The  reaction  of  this  reagent  is  common  to  solutions  of  most  of 
the  alkaloids,  and  also  to  other  organic  principles. 

4.  Potassium  Sulphoeyanide. 

This  reagent  occasions  in  somewhat  strong  solutions  of  salts  of 
codeine  a  white  crystalline  precipitate  of  the  sulphocyanide  of  codeine, 
which,  according  to  Anderson,  has  the  composition  Ci8H2iN03,HCNS. 
The  precipitate  is  readily  soluble  in  acetic  acid. 

1.  yIto   gi'^i'i  o^   codeine :    after  some    minutes   crystalline  needles 

begin  to  separate,  and  after  a  little  time  there  is  a  copious  crys- 
talline deposit,  Plate  VIII.,  fig.  6.  If  the  mixture  be  stirred,  it 
immediately  yields  crystals,  and  very  soon  the  drop  becomes 
a  mass  of  crystalline  groups. 

2.  Tj-J-_  grain  :    on  stirring  the  mixture,  crystals  soon  appear,  and 

after  a  time  there  is  a  very  satisfactory  deposit. 
This  reagent  also  produces  crystalline  precipitates  with  solutions 
of  several  other  alkaloids. 

5.  Potassium  Dichromate. 

Potassium  dichromate  produces  in  quite  strong  solutions  of  salts 
of  codeine  a  yellow  crystalline  precipitate,  which  is  readily  soluble 
in  acetic  acid.  Very  concentrated  solutions  of  the  alkaloid  yield 
beautiful  groups  of  bold,  red  crystals. 

One  grain  of  a  1-1 00th  solution  yields  no  immediate  precipi- 
tate, but,  after  standing  some  time,  crystalline  tufts  separate,  and  the 
mixture  ultimately  becomes  a  nearly  solid  mass  of  crystals,  Plate 
IX.,  fig.  1.  The  formation  of  the  precipitate  is  much  facilitated  by 
stirring  the  mixture. 

Potassium  chromate  produces  with  very  strong  solutions  of  the 
alkaloid  a  yellow  precipitate  of  crystalline  plates  and  prisms. 

6.  Auric  Chloride. 

This  reagent  throws  down  from  solutions  of  salts  of  codeine  a 
reddish-brown  amorphous  precipitate,  which  when  treated  with  caus- 
tic potash  yields  a  dark-bluish  mixture. 
1.  Y^  grain  of  codeine   yields  a  very  copious  precipitate:    after 

standing   some   time,  the  supernatant  fluid  acquires  a  bluish 

color. 


528  OODEINE. 

2.  YoTo  g^^^i°  yields  a  very  good,  yellow  deposit. 

3.  g-^g-g-  grain  yields  a  very  distinct  cloudiness. 

7.  Platinic  Chloride. 

This  reagent  precipitates  from  strong  solutions  of  salts  of  codeine 
a  yellow,  amorphous  deposit,  which  is  readily  soluble  in  acetic  acid, 
but  unchanged  by  caustic  potash. 

1.  ylg-  grain  of  codeine  yields  a  copious  deposit,  which  after  a  time 

becomes  more  or  less  granular. 

2.  -5-^0-  grain  yields  after  several  minutes  a  partly  granular  precipi- 

tate. 

8.  Piei'ic  Acid. 

An  alcoholic  solution  of  picric  acid  produces  in  solutions  of  salts 
of  codeine  a  bright  yellow,  amorphous  precipitate. 

1.  yly-  grain  of  codeine  yields  a  very  copious  deposit. 

2.  Y^oT   g^^ain  :  a  quite  good  precipitate. 

3.  2W0  gi'^^^^  yields  after  a  little  time  a  quite  distinct  cloudiness. 

9.  Nitric  Acid  and  Potassium  Hydrate. 

When  a  small  quantity  of  codeine,  in  its  solid  state,  is  added  to 
a  drop  of  concentrated  nitric  acid,  it  dissolves  with  the  evolution 
of  nitrous  fumes,  yielding  an  orange-yellow  solution,  which,  when 
evaporated  to  dryness  on  a  water-bath,  leaves  a  yellow  residue.  If 
this  residue  be  treated  with  a  drop  of  caustic  potash,  it  acquires  a 
beautiful  orange  color,  and  partially  dissolves  to  a  solution  of  the 
same  hue,  which  is  permanent. 
1_  ^_L_  grain  of  codeine  yields  the  results  just  described. 

2.  YFoT  gJ^aiii  •    the    nitric   acid    solution    leaves  a  slightly  yellow 

residue,  which  with  caustic  potash  yields  a  good  orange-colored 
mixture. 

3.  Yi),-woT  g^^^"  '■  the  slightly  yellow  residue  left  by  the  acid  is  but 

little  changed  by  the  potassium  compound ;  but  if  this  mixture 
be  evaporated,  it  leaves  a  yellowish-orange  deposit,  mixed  with 
crystals  of  potassium  nitrate :  a  drop  of  water  readily  dissolves 
these  crystals,  and  yields  a  yellow-orange  mixture,  the  color  of 
which  is  permanent. 

Potassium  iodide  produces  in  concentrated  solutions  of  salts  of 


NARCEINE.  529 

codeine,  especially  u{)oii  stirring-  the  mixture,  a  crystalline  precipitate 
of  tiif'ts  of  needles,  Plate  IX.,  fig.  2. 

Corrosive  sublimate,  potassium  ferro-  and  ferri-cyanide,  copper 
sulj)hate,  and  silver  nitrate  produce  no  precipitate,  at  least  imme- 
diately, in  a  1-lOOth  solution  of  salts  of  codeine. 

VI.  Narceine. 

HiMory. — Narceine,  which  is  said  to  form  from  six  to  twelve  per 
cent,  of  Smyrna  opium,  was  discovered,  in  1832,  by  Pelletier.  Its 
formula,  according  to  Dr.  Anderson,  is  023^29^^)9.  ^^  seems  to  be 
a  neutral  substance,  yet  it  will  unite  with  acids  to  form  salts,  all 
of  which  have  an  acid  reaction.  The  statements  of  observers  in  re- 
gard to  the  constitution  and  properties  of  narceine  have  been  very 
conHicting,  and  it  is  probable  that  two  or  perhaps  three  different 
substances  have  been  described  under  this  name. 

Preparation. — This  substance  may  be  obtained,  according  to  Dr. 
Anderson  [Quart.  Jour.  Chem.  Soc,  v.  257),  from  the  mother-liquor 
of  hydrochloride  of  morphine  by  diluting  it  with  water,  filtering, 
and  then  adding  ammonia  as  long  as  a  precipitate  is  produced.  Nar- 
ceine and  meconin  remain  in  solution,  while  narcotine,  resin,  and 
small  quantities  of  papaverine  and  thebaine  are  deposited.  The 
filtered  liquid  is  treated  with  excess  of  lead  acetate,  the  dirty-brown 
precipitate  produced  removed  by  a  filter,  the  excess  of  lead  separated 
from  the  filtrate  by  sulphuric  acid,  and  the  liquid  saturated  with 
ammonia,  then  evaporated  at  a  moderate  temperature  to  a  syrup, 
when  it  is  allowed  to  stand  some  days.  The  precipitate  then  formed 
is  collected  on  a  cloth  and  washed  with  water,  then  boiled  with  a 
large  quantity  of  water  and  the  hot  solution  filtered.  On  cooling, 
the  liquid  becomes  filled  with  fine  silky  crystals  of  narceine,  which 
are  separated  from  traces  of  calcium  sulphate  by  solution  in  alcohol, 
and  further  purified  by  boiling  with  animal  charcoal  and  reerystal- 
lization  from  water. 

Physiological  Effects. — Experiments  upon  inferior  animals  indi- 
cate narceine  to  be  an  inert  substance. 

Chemical  Properties. — Narceine  crystallizes  in  beautiful, 
colorless,  delicate  needles,  which  when  dry  form  an  exceedingly 
light,  spongy  mass.  It  is  unchanged  by  persalts  of  iron.  At  a 
moderate  heat  it  fuses  to  a  clear  liquid,  and  at  higher  temperatures 
burns  like  a  resin. 

34 


530  NAECEINE. 

The  narceine  used  in  the  present  investigations  was  prepared 
by  E.  Merck :  it  was  in  the  form  of  very  delicate,  colorless,  silky 
needles. 

Concentrated  sulphuric  add  causes  the  alkaloid  to  assume  a 
reddish-brown  color,  and  dissolves  it  to  a  reddish  or  yellowish-red 
solutioD,  which  upon  the  application  of  a  moderate  heat  acquires 
an  intense  red  color,  and  at  higher  temperatures  darkens.  These 
results,  however,  are  much  influenced  by  the  amount  of  acid  and 
heat  employed.  In  no  instance,  with  the  single  specimen  examined, 
did  we  obtain  the  green  color  described  by  Anderson  {Quart.  Jour. 
Chem.  Soc,  v.  259),  nor,  with  the  diluted  acid,  the  blue  color  ob- 
tained by  other  observers.  A  crystal  of  potassium  nitrate  stirred 
in  the  cold  acid  solution  yields  a  reddish-brown,  violet,  or  purple 
coloration,  according  to  the  relative  quantities  of  the  different  sub- 
stances present :  the  color  is  discharged  by  heat.  Potassium  dichro- 
mate  produces  with  the  acid  solution  a  dirty-red  color,  which  on 
the  application  of  heat  is  changed  to  green,  due  to  the  production 
of  sesquioxide  of  chromium. 

When  treated  with  concentrated  nitrie  acid,  narceine  assumes  an 
orange-red  color  and  dissolves  to  a  more  or  less  yellow  solution, 
which  suffers  little  or  no  change  by  a  moderate  heat.  The  solution 
is  unaffected  by  stannous  chloride,  even  upon  the  application  of  heat. 
The  sample  under  consideration,  when  dropped  into  concentrated 
hydrochloric  acid,  became  blue,  and  dissolved  to  a  perfectly  color- 
less solution.  Pelletier  described  this  reaction  as  characteristic  of 
narceine,  while  Anderson  failed  to  obtain  a  blue  color  from  samples 
which  he  considered  pure. 

When  excess  of  narceine  is  digested,  with  frequent  agitation,  for 
twenty-four  hours  in  water  at  the  ordinary  temperature,  it  requires 
1660  parts  of  the  liquid  for  solution.  It  is  much  more  soluble  in 
hot  water,  from  which  the  excess  slowly  separates  as  the  solution 
cools.  One  part  of  the  alkaloid  dissolves  in  five  hundred  parts  of 
water  as  soon  as  the  mixture  is  brought  to  the  boiling  temperature ; 
this  solution  may  then  be  exposed  for  half  an  hour  or  longer  to  a 
temperature  of  15.5°  C.  (60°  F.)  before  crystals  begin  to  separate. 
A  concentrated  aqueous  solution  of  narceine  has  no  action  upon  red- 
dened litmus.  Absolute  ether,  under  the  foregoing  conditions,  dis- 
solved one  part  of  narceine  in  4066  parts  of  the  liquid.  Chloroform, 
under  similar  circumstances,  dissolved  one  part  in   7950  parts  of 


BROMINE   IN   BROMOHYDRIC   ACID   TEST.  531 

liquid.     It  is  luticli   nioro  soluble  in  iilcoliol  than  in  water,  and  is 
also  somewhat  soluble  in  dilute  solutions  of  the  caustic  alkalies. 

In  the  followinti;  investi^jations,  the  1-lOOtli  solutions  were  ob- 
tained by  the  aid  of  hydrochloric  acid  and  a  gentle  heat;  the  more 
dihite  solutions  were  prepared  l)y  dissolvinjjj  the  narceine,  when 
necessary  by  the  aid  of  heat,  directly  in  distilled  water,  A  1-lOOth 
solution  of  narceine  in  the  form  of  hydrochloride,  unless  main- 
tiiiued  at  a  gentle  temperature,  soon  becomes  filled  with  a  net-work 
of  long,  delicate,  crystalline  needles. 

1.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  produces  in  solution  of 
narceine  a  reddish-yellow  precipitate,  which  almost  immediately  be- 
comes crystalline.  The  precipitate  is  slowly  soluble  in  large  excess 
of  acetic  acid. 

1.  YoT  grain  of  narceine,  in  one  grain  of  water,  yields  a  very  copious 

deposit,  which  very  soon  becomes  a  mass  of  crystalline  needles 
and  tufts;  at  the  same  time  the  mixture  acquires  a  blue  color. 
The  precipitate  is  readily  soluble  in  alcohol,  from  which  it  soon 
again  separates  in  the  crystalline  form. 

2.  yuVu"  grain  yields  a  coj)ious  precipitate,  which  soon  changes  to 

exceedingly  delicate  crystalline  tufts,  Plate  IX.,  fig.  3.  After  a 
time  the  mixture  acquires  a  more  or  less  blue  color. 

3.  5",^  grain  after  a  time  yields  some  few  crystalline  tufts,  of  the 

forms  just  illustrated. 
The  production  of  these  crystalline  tufts  is  quite  peculiar  to 
solutions  of  narceine. 

2.  Bromine  in  Bromohydrio  Acid. 

A  solution  of  bromine  in  bromohydric  acid  throws  down  from 
solutions  of  narceine  a  bright  yellow,  amorphous  precipitate,  which 
after  a  time  dissolves,  but  is  reproduced  upon  further  addition  of  the 
reagent.     The  precipitate  is  soluble  in  acetic  acid  and  in  alcohol. 

1.  Yo  y  grain  of  narceine,  in  one  grain  of  water,  yields  a  very  copious 

precipitate. 

2.  jtjVo  grain  :  a  copious  deposit. 

3.  y^.Voir  grain  yields  after  a  very  little  time  a  quite  fair,  yellow 

precipitate. 


532  NAECEINE. 

3.  Auric  Chloride. 

This  reagent  occasions  in  solutions  of  narceine  a  yellow,  floccu- 
lent  precipitate,  which  remains  unchanged  in  color.  The  precipitate 
is  soluble  in  the  mixture  upon  the  application  of  heat,  and  is  repro- 
duced unchanged  as  the  solution  cools.  It  is  readily  soluble  to  a 
clear  solution  in  potassium  hydrate. 
1_  _i_^  grain  of  narceine  yields  a  very  copious  deposit. 

2.  x^Vo  gi'ain :  a  very  good  precipitate. 

3.  yp-L-g-^  grain  yields  after  a  little  time  a  perceptible  turbidity, 

which  soon  becomes  quite  well  marked.    . 

4.  PlatiniG  Chloride. 

This  reagent  precipitates  from  solutions  of  narceine  a  yellow, 
flocculent  deposit,  which  is  readily  soluble  in  acids.  After  a  time 
the  precipitate  yields  granules  and  crystalline  needles. 

1 .  _i_^  grain  of  narceine  yields  a  very  good  deposit. 

2.  -g  i-g-  grain :  a  very  fair  precipitate. 
3  YoW  grain  :  no  indication. 

5.  Picric  Acid. 

An  alcoholic  solution  of  picric  acid  causes  in  solutions  of  nar- 
ceine a  yellow,  amorphous  precipitate,  which  is  readily  soluble  in 
acetic  acid. 
1_     1^-  2;rain  of  narceine  yields  a  copious  deposit. 

2.  YWWo  gi'ain  :  a  good  precipitate. 

3.  _^  grain  yields  after  a  little  time  a  quite  satisfactory  deposit. 

6.  Potassium  Bichromate. 

This  reagent  produces  in  strong  solutions  of  narceine  a  yellow, 
amorphous  precipitate,  which  soon  becomes  crystalline. 

1.  1^   grain  of  narceine  yields  a  very  copious  precipitate,   which 
almost  immediately  becomes  a  mass  of  crystals. 

2.  -g-i-g-  grain  yields  a  very  good  crystalline  deposit,  Plate  IX.,  fig.  4. 

Potassium  chromate  produces  in  solutions  of  the  alkaloid  much 
the  same  results  as  the  dichromate. 

Potassium  iodide,  potassium  sulphocyanide,  corrosive  sublimate, 


OPIANYL.  533 

potassiinn  ferro-  and  ferri-cyanide,  produce  no  precipitate  in  even 
saturated  aqueous  solutions  of  narceine. 

VII.   Opianyl. 

Hidovij. — Opianyl,  or  Meconine,  n.s  it  was  fornierly  named, 
was  discovered,  in  1826,  by  M.  Dublanc,  but  first  descrilx;d  by  M. 
Couerbe,  in  1832.  It  is  a  neutral  crystal lizable  substance,  and  forms 
less  than  one  per  cent,  of  opium.  Its  formula,  as  first  determined 
by  Couerbe,  and  afterward  confirmed  botii  by  Regnault  and  by  An- 
derson, is  CioHi„0^.  It  therefore  differs  from  the  alkaloids  in  not 
coiitainin*;  nitrogen. 

Preparation. — Opianyl  may  be  obtained  from  the  mother-liquor 
from  which  narceine  has  been  prepared  by  agitating  it  with  suc- 
cessive portions  of  ether,  as  long  as  this  liquid  becomes  colored.  The 
united  ethereal  solutions  are  then  evaporatedy  and  the  brown  syrup 
treated  with  dilute  hydrochloric  acid,  which  dissolves  the  papa- 
verine, while  the  opianyl,  together  with  some  resin,  remains.  The 
opianvl  is  then  crystallized  several  times  from  boiling  water,  with 
the  addition  of  animal  charcoal,  when  it  finally  separates  in  color- 
less needles.  It  may  also  be  obtained  by  acting  upon  narcotine  with 
nitric  acid. 

Physiological  Effects. — From  the  few  experiments  made  with 
this  substance,  it  would  seem  to  be  inert. 

Chemical  Properties. — Opianyl  readily  crystallizes  in  the 
form  of  long,  colorless,  six-sided  prisms,  or  as  delicate  needles;  it 
has  a  somewhat  bitter  taste.  At  a  moderate  heat,  it  fuses  to  a  color- 
less liquid,  which  upon  cooling  solidifies  to  a  radiated  crystalline 
mass  ;  at  higher  temperatures,  it  is  dissipated  in  the  form  of  white 
fumes.  When  cautiously  heated  in  a  glass  tube,  it  sublimes  in  beau- 
tiful crystals  (Anderson).  According  to  Dr.  Guy,  opianyl  fuses  at 
48.8°  C.  (120°  F.),  and  vaporizes  at  82.2°  C.  (180°  F.).  Although 
a  perfectly  neutral  body,  opianyl  is  soluble  in  acids. 

The  following  observations  are  based  upon  the  examination  of  a 
single  specimen  of  opianyl,  prepared  by  E.  Merck.  It  was  in  the 
form  of  delicate,  snow-white  crystals. 

Concentrated  sulphuric  acid  dissolves  it  to  a  colorless  solution, 
w^hich  when  heated  acquires  either  a  beautiful  blue  or  purple  color, 
the  hue  depending  upon  the  relative  quantity  of  acid  employed  (see 


534  OPIANYL. 

post) ;  the  cooled  mixture,  upon  the  addition  of  water,  becomes 
reddish-brown  and  yields  a  brownish  precipitate.  Nitric  acid  also 
dissolves  it  to  a  colorless  solution,  which  on  being  heated  acquires  a 
more  or  less  yellow  color,  and  on  evaporation  leaves  a  colorless  crys- 
talline residue.  It  is  also  soluble  in  concentrated  hydrochloric  acid 
without  change  of  color,  even  upon  the  application  of  heat. 

When  excess  of  opianyl  is  digested  in  water  for  several  hours, 
with  frequent  agitation,  at  a  temperature  of  about  15.5°  C  (60°  F.), 
one  part  dissolves  in  515  parts  of  the  liquid.  According  to  Couerbe, 
it  dissolves  in  265  parts  of  cold  water ;  while  Anderson  states  that 
at  15.5°  C.  (60°  F.)  it  requires  700  parts  of  this  liquid  for  solution. 
It  is  much  more  freely  soluble  in  hot  water,  but  much  of  the  excess 
separates  in  its  crystalline  state  as  soon  as  the  solution  begins  to  cool. 
When  excess  of  opianyl  is  boiled  with  water,  it  melts  under  the 
liquid ;  yet,  according  to  Anderson,  when  in  its  dry  state,  it  requires 
a  temperature  of  110°  C.  (230°  F.)  for  its  fusion.  Absolute  ether, 
when  in  contact  with  excess  of  opianyl  for  several  hours  at  the  ordi- 
nary temperature,  dissolves  one  part  in  136  parts  of  the  liquid. 
Chloroform  dissolves  it  in  all  proportions.  It  is  also  readily  solu- 
ble in  alcohol;  but  it  is  not  more  soluble  in  solutions  of  the  caustic 
alkalies  than  in  pure  water. 

In  the  following  investigations,  the  opianyl  was  dissolved,  when 
necessary  by  the  aid  of  a  very  gentle  heat,  in  pure  water. 

1.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  produces  in  aqueous 
solutions  of  opianyl  a  yellowish-brown,  amorphous  precipitate,  which 
quickly  becomes  quite  dark  brown,  and  then  changes  to  a  mass  of 
yellow  crystals,  which  in  their  dry  state  resemble  spangles  of  gold- 
dust.     The  precipitate  is  readily  soluble  in  alcohol. 

1.  -g-l^  grain  of  opianyl,  in  one  grain  of  water,  yields  a  very  copious 

precipitate,  which  very  soon  becomes  converted  into  yellow  crys- 
tals, Plate  IX.,  fig.  5. 

2.  YWo"  S^^^^  •  ^  good,  yellowish-brown  deposit,  which  soon  darkens. 

3.  -aFoT  grain  yields  after  a  little  time  a  slight  cloudiness,  followed 

by  the  precipitation  of  dark-colored  granules. 
The  reaction  of  this  reagent  is  quite  peculiar  to  solutions  of 
opianyl. 


.SULPHURIC   ACID   TEST.  535 

2.  Bromine  in  Bromohydric  Add. 

This  reagent  precipitates  from  solutions  of  opianyl  a  deposit  of 
short  needles,  and  groups  of  hair-like  crystals.  The  precipitiite  is 
insoluble  in  acetic  acid,  and  hut  slowly  soluble  in  large  excess  of 
alcohol. 

1.  -j-J^y  grain  :  after  a  few  nionients  crystals  begin  to  form,  and  soon 

there  is  a  quite  copious  deposit,  Plate  IX.,  fig.  6 ;  after  a  time 
the  mixture  becomes  a  colorless  mass  of  crystals. 

2.  -Yy}\)\)   gi'ain  :    in    a   very   little    while  a   quite   good    crystalline 

deposit. 

3.  yTTUir  g^^i"  yields  after  a  little  time  a  very  satisfactory  crystal- 

line precipitate. 
The  production  of  this  crystalline  precipitate  is  quite  character- 
istic of  opianyl. 

3.  Sulphuric  Acid  and  Heed. 

When  a  small  quantity  of  opianyl  in  its  solid  state  is  heated 
"with  a  very  minute  portion  of  concentrated  sulphuric  acid,  it  yields 
an  intense  blue  color,  which,  as  the  heat  is  increased,  changes  to 
purple ;  when  a  larger  quantity  of  acid  is  employed,  the  heated 
mixture  acquires  a  transient  blue  color,  which  passes  to  purple; 
while  with  a  still  larger  quantity  the  mixture,  when  heated,  assumes 
at  once  a  beautiful  purple  color.  This  experiment  may  be  performed 
in  a  thin,  annealed  watch-glass. 

1.  ^Jpy  grain  of  opianyl,  when  moistened  with  a  very  small  quantity 

of  the  acid,  and  heated,  yields  an  intense  blue  coloration. 

2.  ydVo-  grain  :  much  the  same  as  1.     For  the  success  of  this  reac- 

tion it  is  essential  that  the  least  possible  quantity  of  acid  be 
employed.  This  is  best  attained  by  touching  the  deposit  with  a 
glass  rod  moistened  with  the  acid;  the  mixture  is  then  heated 
over  the  flame  of  a  spirit-lamp,  until  it  begins  to  assume  a  blue 
color, — which  does  not  usually  occur  until  vapors  of  the  acid 
are  evolved, — when  the  heat  is  withdrawn. 

3.  xir.Vro  grain,  when  treated  as  just  described,  yields  very  satisfac- 

tory results. 

4.  Yohwo  gi'ain  :  if  the  deposit  be  not  distributed  over  a  large  space, 

it  yields  a  very  distinct  blue  coloration. 
With  a  very  small  quantity  of  the  acid,  a  blue  color  may  be 


536  OPIANYL. 

obtained  from  a  much  less  quantity  of  opianyl  than  will  yield  a 
purple  color  with  a  larger  quantity  of  the  acid.  The  production 
of  this  blue  coloration  is  quite  characteristic  of  opianyl.  Narcotine 
when  heated  with  a  small  quantity  of  sulphuric  acid  yields  a  purple 
mixture,  which  darkens  as  the  heat  is  increased.  So,  also,  a  sul- 
phuric acid  solution  of  codeine,  when  heated,  acquires  a  purple  color. 
A  sulphuric  acid  solution  of  opianyl,  when  stirred  with  a  few 
crystals  of  potassium  nitrate,  yields  a  yellow  mixture,  soon  changing 
to  a  beautiful  scarlet-orange  color,  which  but  slowly  fades.  Almost 
the  least  visible  quantity  of  the  substance,  when  treated  in  this  man- 
ner with  a  very  small  quantity  of  the  acid  and  nitre,  yields  very 
satisfactory  results.  On  heating  the  mixture,  the  orange  color  is 
changed  to  yellow.  In  these  reactions  opianyl  somewhat  resembles 
narcotine. 

As  opianyl  forms  no  definite  combinations  with  acids  or  with 
the  metals,  it  is  not  precipitated  by  the  ordinary  reagents.  Accord- 
ing to  Couerbe,  it  yields  a  crystalline  precipitate  with  basic  lead 
acetate ;  but,  like  Anderson,  we  failed  to  obtain  a  precipitate  by  this 
reagent. 


NUX   VOMICA.  537 


CHAPTEE    III. 

NUX   VOMICA,   STRYCHNINE,   BJiUCINE. 

I.  Nux  Vomica. 

Histcrry  and  Composition. — Nux  vomica  is  the  seed  of  the 
Strychnos  nux  vomica,  a  tree  found  native  in  the  East  Indies  and 
the  ishind  of  Ceylon.  The  seeds  are  flat,  nearly  round,  and  some- 
thing less  than  an  inch  in  diameter,  being  slightly  concave  on  one 
side,  and  convex  on  the  other,  and  covered  with  short,  silky,  grayish 
or  vellowish  hairs,  which  are  attached  to  an  investing  membrane 
and  incline  towards  the  circumference  of  the  seed.  The  seeds  are 
very  hard,  diflScult  to  pulverize,  and  when  chewed  have  an  intensely 
bitter  taste,  but  they  are  destitute  of  any  well-marked  odor.  In  its 
powdered  state  nux  vomica  has  a  yellowish-gray  color,  and  a  peculiar 
odor,  not  very  unlike  that  of  liquorice. 

Nux  vomica  possesses  powerful  poisonous  properties,  due  to  the 
presence  of  the  alkaloids  strychnine  and  bnicine,  which  exist  in  the 
seed  in  combination  with  a  peculiar  organic  acid,  known  as  strychnic, 
or  igasuric,  acid.  The  seeds  also  contain,  according  to  the  analysis 
of  Pelletier  and  Caventou,  yellow  coloring  matter,  gum,  a  waxy 
substance,  starch,  a  concrete  oil,  woody  fibre,  and  earthy,  salts.  A 
third  alkaloid,  under  the  name  of  igasurine,  was  described  by  M. 
Desnoix.  But,  according  to  W.  A.  Shenstone  {Jou7\  Chem.  Soc, 
Sept.  1881,  453),  the  substance  thus  described  is  nothing  more  than 
impure  bnicine.  The  powdered  seeds  yield  their  active  properties 
to  water,  but  much  more  freely  to  alcohol.  Poisoning  by  this  sub- 
stance has  been  of  quite  frequent  occurrence. 

Symptoms. — The  symptoms  produced  by  poisonous  doses  of  nux 
vomica,  or  either  of  its  active  alkaloids,  are  very  uniform  in  their 
nature,  and  quite  peculiar.     There  is  at  first  a  sense  of  numbness  in 


538  NUX   VOMICA. 

the  extremities,  with  more  or  less  trembling  of  the  muscles,  and  a 
feeling  of  great  anxiety.  These  effects  are  soon  succeeded  by  violent 
muscular  contractions,  in  which  the  limbs  are  extended  and  perfectly 
rigid,  the  head  thrown  back,  the  jaws  fixed,  the  face  livid,  and  the 
respiration  apparently  suspended.  After  a  little  time,  varying  from 
a  few  moments  to  some  minutes,  the  convulsive  paroxysm  subsides, 
and  the  patient  then  feels  much  exhausted,  and  is  usually  extremely 
sensitive  to  external  impressions.  This  condition,  however,  is  usually 
of  short  duration,  the  convulsions  being  succeeded  by  others,  which 
increase  in  violence,  and  speedily  run  to  a  fatal  termination.  In 
some  instances  death  takes  place  during  a  paroxysm,  but  more  gen- 
erally from  extreme  exhaustion.  The  intellectual  faculties  usually 
remain  unaffected,  even  up  to  the  time  of  death.  The  time  within 
which  the  symptoms  first  manifest  themselves  is  subject  to  con- 
siderable variation,  they  occurring  in  some  instances  almost  imme- 
diately, and  in  others  being  delayed  for  even  more  than  an  hour. 

The  following  case,  reported  by  Mr.  Oilier,  well  illustrates  the 
usual  effects  of  uux  vomica.  A  young  woman  purposely  swallowed, 
in  suspension  in  water,  about  three  drachms  of  the  powder.  When 
seen  about  half  an  hour  afterward,  she  was  calm  and  quite  well. 
But  in  about  ten  minutes  more  she  was  seized  with  a  convulsive  fit, 
and  in  a  few  minutes  afterward  had  another,  which  was  soon  suc- 
ceeded by  a  third  :  the  duration  of  these  paroxysms  was  about  two 
minutes  each.  During  the  attacks  the  whole  body  was  extended 
and  rigid,  the  legs  widely  separated,  the  face  and  hands  livid,  and 
the  muscles  of  the  former  violently  convulsed  :  no  pulse  or  breathing 
could  be  perceived.  In  the  intervals  she  was  quite  sensible ;  com- 
plained of  being  sick,  and  made  many  attempts  to  vomit;  had  in- 
cessant thirst,  a  very  quick  and  feeble  pulse,  and  perspired  freely. 
A  fourth  attack  soon  followed,  in  which  the  whole  body  was  ex- 
tended to  the  utmost  and  rigidly  stiff.  She  now  fell  into  a  state  of 
asphyxia,  relaxed  her  grasp,  white  foam  issued  from  her  mouth,  the 
expression  of  the  countenance  became  most  frightful,  and  death 
ensued  in  about  an  hour  after  the  poison  had  been  taken.  (London 
Med.  Repository,  xix.  448.) 

In  a  non-fatal  case  related  by  Dr.  Basedow,  of  Merseburg,  the 
following  symptoms  were  observed.  A  young  lady  took  by  mistake 
a  tablespoonful  of  the  powdered  drug.  She  was  almost  instantly 
deprived  of  the  power  of  walking,  and  fell  down,  but  still  retained 


PERIOD    WHEN    FATAL.  539 

her  consciousness.  When  first  seen  by  Dr.  Basedow,  almost  imme- 
diately afterward,  her  connteiiaiu'C  was  pale,  and  exhibited  alternately 
an  expression  of  indiilcrence  and  anxiety  ;  the  eyes  were  wide  open, 
and  the  pupils  contracted.  The  respiration  was  irregular  and  short; 
the  pulse  irregular  and  small,  and  the  skin  cool.  The  forearms  were 
coustantlv  in  a  half-bent  position,  and  the  hands  and  lingers  affected 
with  convulsive  twitches;  but  the  legs  were  motionless  and  rigid,  all 
the  muscles  being  hard  and  tetanically  contracted.  The  patient  had 
not  the  slightest  jniin  or  sickness;  but  her  breathing  became  every 
moment  more  difficult,  and  she  complained  of  impending  suffoca- 
tion. An  emetic  was  now  administered,  and  its  action  followed  by 
the  exhibition  of  small  doses  of  a  mixture  of  oil  of  turpentine  and 
sulphuric  ether.  The  dyspnoea  gradually  subsided,  and  in  about  six 
hours  after  the  poison  had  been  taken  the  tetanic  spasms  of  the  mus- 
cles of  the  legs,  as  well  as  the  convulsive  movements  of  the  hands, 
had  ceased,  and  the  respiration  was  free;  but  the  patient  complained 
of  a  sense  of  bruising  over  the  whole  body,  and  pain  in  the  limbs, 
for  some  days  afterward.  {New  York  Med.  and  Phys.  Journal,  xxx. 
448.) 

In  some  few  of  the  recorded  cases  of  poisoning  by  this  sub- 
stance, the  first  symptoms  observed  were  nausea  and  vomiting; 
while  in  others  the  tetanic  symptoms  were  followed  by  purging,  and 
inflammation  of  the  stomach  and  bowels. 

Period  when  Fatal. — In  fatal  poisoning  by  nux  vomica,  death 
usually  takes  place  within  a  very  few  hours  after  the  poison  has  been 
taken  ;  but  life  has  been  prolonged  for  some  days.  In  a  case  cited 
by  Dr.  Christisou,  in  which  a  man  swallowed  an  unknown  quantity 
of  the  powder  mixed  with  beer,  death  occurred  in  fifteen  minutes 
after  the  poison  had  been  taken.  [On  Poisons,  686.)  Several  in- 
stances are  related  in  which  death  took  place  in  from  one  to  two 
hours.  On  the  other  hand,  in  a  case  cited  by  Orfila  {Toxicologie, 
ii.  605),  a  man  swallowed  a  considerable  quantity  of  the  powder,  and 
almost  immediately  was  seized  with  violent  convulsions ;  yet  death 
did  not  occur  until  the  fourth  day. 

Fatal  Quantity. — In  a  case  quoted  by  Dr.  Christison,  an  old 
woman  who  was  using  an  alcoholic  extract  of  nux  vomica  for  palsy 
took  an  overdose  of  three  grains,  which  soon  produced  violent  tetanic 
spasms,  followed  by  an  attack  of  inflammation  of  the  stomach  and 
intestines,  and  death  on  the  third  day.     The  quantity  of  the  crude 


540  NUX   VOMICA. 

powder  represented  by  the  extract  taken  in  this  case  is  quite  uncer- 
tain. In  another  case,/oitr  gi^ains  of  the  extract  taken  by  a  lady, 
through  the  mistake  of  a  druggist,  caused  her  death  within  a  few 
hours.  [Amer.  Jour.  Pharm.,  July,  1867,  379.)  In  an  instance  re- 
lated by  Hoffmann,  thirty  grains  of  the  crude  powder,  taken  in  two 
equally  divided  doses,  caused  death.  Dr.  Taylor  mentions  two  cases, 
in  each  of  which  fifty  grains  of  the  powder  proved  fatal :  in  one  of 
these,  death  took  place  in  an  hour.  {On  Poisons,  767.)  In  another 
instance,  two  drachms  caused  death  in  about  two  hours. 

A  boy,  aged  twelve  years,  took  into  his  mouth  about  eight  grains 
of  the  extract,  thinking  it  was  liquorice.  Finding  it  very  bitter,  he 
spat  out  as  much  as  he  could.  About  an  hour  later,  there  were  some 
slight  twitchings  of  the  muscles,  and  soon  after,  well-marked  opis- 
thotonos, with  an  increase  of  the  spasms,  and  the  face  was  flushed  and 
anxious.  The  patient  was  aware  of  the  approach  of  the  spasms, 
saying,  "It's  coming;"  and  there  was  a  sense  of  impending  death, 
he  saying,  "  Good-by  ;  I'm  dying."  Under  treatment,  the  boy  re- 
covered within  a  few  days.  {Guy's  Hosp.  Rep.,  xiv.  266.)  Recovery 
has  not  unfrequently  taken  place  after  comparatively  large  quantities 
of  nux  vomica  had  been  swallowed. 

Teeatment. — The  stomach  should  be  emptied  as  speedily  as  pos- 
sible, either  by  means  of  the  stomach-pump  or  by  the  administration 
of  an  emetic.  Since  the  poison,  when  taken  in  the  form  of  powder, 
sometimes  adheres  tenaciously  to  the  walls  of  the  stomach,  the  use  of 
the  pump,  or  the  action  of  the  emetic,  should  be  continued  for  some 
time.  Various  chemical  antidotes  have  been  advised,  but  none  of 
these  are  reliable.  After  the  contents  of  the  stomach  have  been 
evacuated,  vegetable  astringents,  or  a  solution  of  iodine  in  potas- 
sium iodide,  might  be  found  useful  for  the  purpose  of  neutralizing 
any  remaining  portions  of  the  poison.  Other  methods  of  treatment 
will  be  referred  to  hereafter,  when  considering  the  antidotes  for 
poisoning  by  strychnine. 

PoST-MOETEM  ApPEAEANCES. — Nux  vomica  may  occasion  death 
without  leaving  any  well-marked  morbid  change  in  any  part  of  the 
body.  In  Mr.  Ollier's  case,  before  cited,  in  which  death  took  place 
in  an  hour,  five  hours  after  death  the  body  was  as  straight  and  stiff 
as  a  statue,  so  that  if  one  of  the  hands  was  moved  the  whole  body 
moved  with  it.  On  dissection,  the  stomach  was  found  nearly  natural, 
the  blood-vessels  of  the  brain  congested,  and  the  heart  of  a  pale  color, 


CHEMKAL    PIIOPERTIES,  641 

t-mply,  and  ilaccid.  In  another  case,  in  wliidi  ahont  an  ounce  (tf  the 
poison  had  been  taken  and  proved  rapidly  fatal,  large  (piantities  of 
a  sangninok'nt  fluid  were  found  in  the  cavities  of  the  brain  and  be- 
tween its  membranes  ;  and  the  lungs,  as  well  as  the  heart,  were  highly 
gorged  with  black  lluid  blood.  The  stomach  was  healthy,  except  a 
j)atch  of  the  nuicous  membrane  in  the  larger  curvature  of  the  organ, 
which  was  evidently  inflamed,  and  of  a  deep  red  color,  the  intensity 
diminishing  from  the  circumference  to  the  centre. 

In  the  case  cited  from  Orfila,  in  whidi  death  did  not  take  place 
until  the  fourth  day,  tlie  following  appearances  were  observed  forty- 
eight  hours  after  death.  The  body  was  considerably  rigid,  and  of  a 
violet  hue.  The  lateral  ventricles  of  the  brain,  and  the  cavity  of 
the  arachnoid  membrane,  contained  large  quantities  of  serum;  but  no 
a})preciable  alteration  was  detected  in  either  the  meninges  or  the  cere- 
bral substance.  The  internal  surface  of  the  stomach  presented  at 
different  points  a  color  which  varied  from  red  to  deep  black  ;  and  the 
duodenum  and  upper  portious  of  the  small  intestines  were  manifestly 
inflamed.    The  lungs  were  gorged  with  blood  ;  the  heart  was  natural. 

Chemicai-  Properties. 

The  physical  properties  of  nux  vomica,  when  'in  its  solid  state, 
readily  distinguish  it  from  all  other  substances.  If  a  small  portion 
of  the  powdered  seed  be  moistened  with  a  drop  of  water,  and  exam- 
ined under  a  low  power  of  the  microscope,  the  broken  fibrous  hairs 
may  be  readily  distinguished,  they  apparently  forming  a  large  por- 
tion of  the  powder.  The  hairs  acquire  a  yellow  color  upon  the 
addition  of  a  solution  of  iodine  in  potassium  iodide;  when  the  crude 
powder  is  thus  treated,  it  assumes  a  deep  brown  color.  When 
touched  with  a  drop  of  concentrated  nitric  acid,  the  powder  acquires 
a  deep  orange-red  color,  which  is  slowly  discharged  by  a  solution  of 
stannous  chloride.  Concentrated  sulphuric  acid  causes  it,  like  most 
vegetable  powders,  to  assume  a  brownish,  then  black  color.  Hydro- 
chloric acid  produces  little  or  no  change.  When  moderately  heated, 
the  powder  evolves  dense,  white  fumes  having  a  peculiar  odor ;  at 
higher  temperatures  it  becomes  ignited. 

When  powdered  nux  vomica  is  macerated  in  water  or  diluted 
alcohol,  the  liquid  takes  up  the  strychnine  and  brucine,  as  salts  of 
their  peculiar  acid,  and  more  or  less  coloring  matter:  this  extraction 
is  much  facilitated  by  a  moderate  heat.     The  solution  thus  obtained 


542  STRYCHNINE. 

has  an  intensely  bitter  taste,  strikes  a  red  color  with  nitric  acid, 
and  yields  a  copious  reddish-brown  precipitate  with  a  solution  of 
iodine  in  potassium  iodide.  It  acquires  a  greenish  hue  when  treated 
with  a  solution  of  a  ferric  salt;  ammonio-copper  sulphate  produces 
a  somewhat  similar  coloration,  and,  after  a  time,  a  greenish-white 
precipitate.  Tannic  acid  throws  down  from  the  solution  a  copious, 
dirty-white  precipitate. 

It  is  obvious  that  there  can  be  no  chemical  test  by  which  the 
presence  of  nux  vomica  as  a  whole,  when  in  a  complex  organic  mix- 
ture, can  be  directly  shown ;  but  this  may  be  inferred  by  proving 
the  presence  of  one  or  more  of  its  peculiar  principles.  Of  these 
principles,  strychnine  is  usually  much  the  most  easy  of  detection. 
Since,  however,  this  alkaloid  is  so  frequently  met  with  in  its  pure 
state,  or  that  of  some  of  its  salts,  its  mere  detection  would  not, 
independent  of  other  circumstances,  prove  the  presence  of  nux  vom- 
ica. The  methods  for  the  separation  of  strychnine  and  brucine 
from  organic  mixtures  of  the  crude  drug  are  the  same  as  those  for 
their  recovery  from  organic  mixtures  in  general,  as  will  be  pointed 
out  hereafter  under  the  special  consideration  of  these  alkaloids. 

II.  Stryehniiie. 

History. — Strychnine,  or  strychnia,  was  discovered,  in  1818,  by 
Pelletier  and  Caventou,  both  in  the  seed  of  Strychnos  nux  vomica 
and  the  St.  Ignatius'  bean,  which  latter  is  the  seed  of  the  Strychnos 
Ignatii.  Thus  far  it  has  been  found  only  in  five  species  of  the 
Strychnos  genus  of  plants,  and  in  most  of  these  it  is  accompanied 
by  brucine.  Several  of  the  species  of  this  genus  of  plants  con- 
tain neither  strychnine  nor  brucine.  The  composition  of  strychnine, 
in  its  anhydrous  state,  according  to  Regnault,  and  since  confirmed 
by  Nicholson  and  Abel,  is  C21H22N2O2 ;  molecular  weight  334.  Ac- 
cording to  most  analysts,  strychnine  forms  something  less  than 
one-half  per  cent,  by  weight  of  nux  vomica ;  Mr.  Horsley,  however, 
states  that  he  obtained  about  one  per  cent,  of  the  alkaloid  from 
that  substance.  From  the  St.  Ignatius'  bean  Pelletier  and  Caventou 
obtained  from  one  to  two  per  cent,  of  the  alkaloid. 

Preparation. — Strychnine  may  be  obtained  from  nux  vomica  by 
the  following  process.  The  rasped  seeds  are  digested  for  twenty- 
four  hours  in  water  acidulated  with  hydrochloric  acid,  the  decoction 
then  strained  through  linen,  the  strained  liquid  concentrated  to  a 


PHYSIOLOGICAL   EFFECTS.  543 

small  voluiMc,  ami  tlicn  j)recipi(at('(l  with  milk  of"  liruo;  the  pre- 
cipitate tliiis  produced  is  collected  on  a  cloth,  washed  with  cold 
water,  tlien  dried,  and  the  pulverized  nia.ss  exhausted  witli  suc- 
cessive portions  of  alcohol  until  dej>rived  of  its  bitterness.  The 
mixed  alcoholic  liquids  are  concentrated  on  a  water-i>ath,  and  then 
treated  with  water  containino;  a  little  sulphuric  acid,  by  which  the 
strvchnine  will  be  dissolved  in  the  form  of  sulphate.  This  solution 
is  boiled  with  animal  charcoal,  filtered,  concentrated  to  a  small 
volume,  and  the  alkaloidal  sulphate  allowed  to  sejiarate  by  crystal- 
lization. The  crystals  may  now  be  dissolved  in  pure  water,  and  the 
alkaloid  precipitated  by  slight  excess  of  ammonia,  then  collected  on 
a  filter,  Avashed  with  cold  water,  and  allowed  to  dry.  As  thus  ob- 
tained, strychnine  usually  contains  more  or  less  brucine. 

Mr.  Horsley's  method  for  preparing  the  alkaloid  consists  in  first 
exhausting  powdered  nux  vomica  by  repeated  extractions  with  water 
strongly  acidulated  with  acetic  acid.  The  united  acid  liquids  are 
then  filtered,  and  the  filtrate  evaporated  to  a  syrupy  consistency. 
The  cooled  residue  is  diluted  with  water,  slight  exce&s  of  ammonia 
added,  and  the  mixture  allowed  to  re])Ose  for  one  or  two  days.  Any 
crystals  thus  obtained  are  washed,  dried,  then  redissolved  in  water 
containing  acetic  acid,  and  the  solution  filtered.  The  liquid  is  now 
treated  with  a  solution  of  potassium  chromate,  by  which  the  alkaloid 
is  precipitated  as  strychnine  chromate.  This  is  collected,  washed, 
then  digested  in  a  solution  of  ammonia,  when,  the  chromic  acid 
uniting  with  the  ammonia,  the  strychnine  separates  in  its  pure  state. 

Strychnine  is  one  of  the  most  virulent  poisons  known.  It  is 
found  in  the  shops  both  in  its  free  state  and  in  the  form  of  some  of 
its  salts ;  its  principal  salts  are  the  sulphate,  the  hydrochloride,  or 
muriate,  and  the  acetate.  The  ordinary  medicinal  dose  of  strych- 
nine, or  of  any  of  its  saline  combinations,  is  about  one-sixteenth  of 
a  grain. 

Symptoms. — These  are  the  same  in  kind  as  those  produced 
by  nux  vomica,  but  they  usually  manifest  themselves  even  more 
promptly.  The  first  symptoms  are  usually  a  sense  of  oppression 
and  great  anxiety,  with  quivering  and  spasmodic  movements  of  the 
muscles  of  the  extremities.  These  effects  are  sooner  or  later  suc- 
ceeded by  violent  muscular  convulsions,  in  which  the  head  is  thrown 
back,  and  the  whole  body  is  rigidly  stiff,  the  extremities  being  ex- 
tended, the  hands  firmly  clinched,  and  the  feet  arched.      In   this 


544  STEYCHNIiSrE. 

state,  the  jaws  are  usually  firmly  closed,  the  eyes  prominent,  the 
pupils  dilated,  the  face  livid,  the  expression  anxious,  and  often 
foam  issues  from  the  mouth ;  the  muscles  of  the  chest  and  dia- 
phragm are  also  strongly  contracted,  and  the  respiration  is  appar- 
ently arrested  ;  the  pulse  is  either  very  rapid  or  altogether  imper- 
ceptible. In  a  little  time,  varying  from  less  than  a  minute  to 
several  minutes,  this  tetanic  condition  usually  entirely  disappears, 
and  there  is  a  state  of  calm.  During  this  state  the  patient  feels 
extremely  weak,  usually  experiences  great  thirst,  and  is  sometimes 
inclined  to  sleep.  After  a  little  time,  however,  the  system  again 
becomes  excited,  the  special  senses  being  exceedingly  acute,  and 
frequently  there  is  a  sense  and  declaration  of  impending  death.  A 
second  paroxysm  may  now  be  induced  by  very  slight  causes,  or  it 
may  appear  wnthout  any  apparent  cause.  Not  unfrequently  the 
patient  is  perfectly  conscious  of  the  approach  of  the  attack,  and 
desires  to  be  held  or  rubbed.  After  a  succession  of  attacks,  varying 
from  two  to  several,  death  takes  place  either  during  a  paroxysm 
from  asphyxia,  or,  more  frequently,  soon  after  from  complete  ex- 
haustion. The  interval  between  the  paroxysms  has  varied  from  a 
few  minutes  to  more  than  half  an  hour.  The  intellect  usually 
remains  clear  up  to  the  time  of  death. 

In  a  case  reported  by  Dr.  Blumhardt,  in  which  a  young  man,  for 
the  purpose  of  self-destruction,  swallowed  forty  grains  of  strychnine, 
the  following  symptoms  were  observed.  The  patient  soon  experienced 
great  anxiety  and  agitation,  and  after  the  lapse  of  fifteen  minutes,  an 
emetic  having  been  administered,  but  with  the  effect  of  producing 
only  slight  vomiting,  he  lay  stiff  upon  his  back,  with  the  head  some- 
what bent  backwards ;  the  lower  extremities  were  perfectly  stiff,  but 
the  upper  still  free ;  the  countenance  was  pale  and  haggard  ;  the  pulse 
quick  and  contracted.  He  still  spoke  with  a  firm  voice  and  in  a  col- 
lected manner,  but  trismus  was  evidently  commencing.  The  attacks 
soon  became  more  violent,  and  the  spasms  extended  to  the  muscles  of 
the  chest ;  the  thorax  appeared  compressed,  and  the  respiration  was 
impeded.  The  paroxysms  were  now  repeated  at  intervals  of  about  a 
minute,  for  a  short  time,  when  the  whole  body  became  affected  and 
as  stiff  as  a  board.  The  suffocation  was  now  extreme ;  the  jaws  firmly 
locked  together ;  the  upper  extremities  firmly  flexed  at  the  elbow-joints 
and  applied  across  the  chest ;  the  lower  extremities  extended  and  stiff, 
and  the  soles  of  the  feet  concave.     By  degrees  the  resj^iration  became 


PHYSIOLOGICAL    EFFECTS.  545 

more  une(|iial,  and  liiially  ccasod  ;  the  pulse  hecaiiui  imperceptible; 
the  skin  of  a  dusky  hlue  coh)r ;  the  face  deep  purple ;  the  eyes  promi- 
nent, and  the  pupils  dilated  and  insensible.  All  signs  of  conscious- 
ness soon  disappeared,  and  the  patient  lay  for  a  few  minutes  without 
motion,  in  a  state  of  universal  tetanus.  A  remission  of  the  convul- 
sions now  suddenly  manifested  itself;  the  limbs  became  relaxed,  and 
after  a  long,  deep-drawn  inspiration  the  pulsations  of  the  heart  and 
arteries  were  again  perceptible ;  consciousness  and  the  power  of  speech 
were  also  restored,  but  the  articulation  was  imperfect.  After  about 
fifteen  minutes  the  patient  was  again  seized  with  a  shivering  fit, 
followed  by  general  tetanus,  which  soon  terminated  in  a  state  of 
asphyxia,  and  death  took  place  an  hour  and  a  half  after  the  poison 
had  been  taken.     {American  3Ied'ical  Intelligencer,  ii.  28.) 

The  following  case  of  recovery  is  related  by  Dr.  Powel.  {Lancet, 
Aug.  1861,  169.)  A  woman,  aged  twenty-eight  years,  took  not  less 
than  two  or  three  grains  of  strychnine  on  an  empty  stomach.  When 
first  seen  by  the  physician,  over  half  an  hour  afterward,  she  was 
lying  on  her  back  on  the  floor,  quite  sensible  ;  the  arms  and  legs  were 
stretched  out  to  their  fullest  extent ;  hands  clinched ;  toes  flexed ; 
legs  close  together,  and  the  body  in  a  state  of  opisthotonos.  The 
countenance  was  livid  and  anxious ;  the  eyes  staring  and  fixed, 
pupils  widely  dilated,  conjunctivae  highly  injected ;  teeth  firmly 
clinched.  The  breathing  was  irregular,  and  at  times  almost  ceased; 
skin  hot,  and  bathed  in  perspiration  ;  pulse  rapid  and  scarcely  per- 
ceptible. The  spasms  relaxed  at  times,  but  did  not  entirely  cease 
for  one  minute.  On  the  slightest  touch  of  the  body  or  legs,  or  on  an 
attempt  to  give  her  drink,  she  would  cry  out,  "My  legs!  my  legs! 
hold  me  !  hold  me  I"  then  utter  a  shriek,  and  quickly  relapse  into  a 
most  violent  spasm  involving  the  entire  body.  Under  the  adminis- 
tration of  chloroform  the  convulsions  became  less  severe.  While 
under  the  influence  of  the  anaesthetic,  an  emetic  was  administered, 
and  produced  some  vomiting.  For  some  hours  the  spasms  recurred 
about  every  five  minutes,  but  with  decreasing  severity,  and  finally 
the  woman  fully  recovered. 

In  a  few  of  the  reported  cases  of  strychnine  poisoning,  the  first 
symptom  observed  was  the  utterance  of  a  loud  cry  or  shriek;  and  at 
least  two  instances  are  recorded  in  which  the  tetanic  symptoms  were 
preceded  by  vomiting.  (Dr.  J.  St.  Clair  Gray,  Strychnia,  1872,  46.) 
In  an  instance  of  the  former  kind,  in  which  we  were  recently  consulted. 


546  STRYCHNINE. 

a  woman  about  her  ordinary  work  suddenly  exclaimed,  Oh!  and 
quickly  fell,  saying  her  feet  had  given  out ;  violent  tetanic  symptoms 
speedily  ensued,  followed  by  death. 

The  time  within  which  the  symptoms  first  manifest  themselves 
in  strychnine  poisoning  has  varied  from  a  few  minutes  to  some  hours ; 
but  they  do  not  often  appear  much  before  fifteen  minutes,  nor  are 
they  often  delayed  much  beyond  half  an  hour.  In  a  case  reported 
by  Dr.  G.  F.  Barker  {Amer.  Jour.  3Ied.  Sci.,  Oct.  1864,  399),  a  young, 
healthy,  married  woman  had  administered  to  her,  with  criminal  intent, 
not  exceeding  six  grains  of  strychnine,  and  violent  symptoms  were 
present  in  th^^ee  minutes  afterward ;  these  were  succeeded  by  several 
convulsive  paroxysms,  and  death  during  a  paroxysm  in  thirty  minutes 
after  the  poison  had  been  taken.  In  this  instance  the  strychnine  was 
taken  in  its  dry  state  into  the  mouth  and  washed  down  with  water. 
This  is  perhaps  the  most  rapid  case,  in  regard  to  the  a})pearance  of 
the  symptoms,  yet  recorded.  In  the  case  of  Dr.  Warner,  of  Ver- 
mont, who  by  mistake  took,  it  is  believ^ed,  something  less  than  half 
a  grain  of  the  poison,  well-marked  symptoms  were  present  within 
five  minutes,  and  death  occurred  in  about  eighteen  minutes.  In  at 
least  three  other  cases  the  symptoms  were  about  equally  prompt  in 
appearing. 

On  the  other  hand.  Dr.  H.  G.  Thomas,  of  Alliance,  Ohio,  has 
reported  a  case  in  which  a  man  swallowed  jive  grains  of  strychnine, 
and  one  hour  and  three-quarters  elapsed  before  any  symptoms  mani- 
fested themselves ;  and,  under  the  use  of  emetics,  the  patient  recov- 
ered. One  of  the  most  remarkable  cases  of  this  kind  yet  recorded 
is  the  following,  reported  by  Dr.  T.  Anderson.  A  gentleman  took 
by  mistake,  believing  it  to  be  a  salt  of  morphine,  three  grains  and  a 
half  of  strychnine,  and  experienced  no  particular  symptoms  until  two 
hours  and  a  half  afterward,  when  he  suddenly  fell  backwards ;  but, 
on  being  immediately  raised,  he  was  able  to  walk  home,  although 
exceedingly  nervous  and  alarmed.  He  soon  felt  better,  and  in  five 
hours  after  taking  the  dose  he  again  took  a  similar  quantity.  In  less 
than  ten  minutes  after  taking  the  last  dose  he  was  seized  with  violent 
tetanic  spasms,  which  continued,  with  the  usual  intermissions,  for 
several  hours,  after  which  he  entirely  recovered.  {Amer.  Jour.  Med. 
Sci.,  April,  1848,  562.)  The  form  in  which  the  poison  is  taken,  and 
the  condition  of  the  stomach,  may  to  some  extent  determine  the  time 
at  which  the  symptoms  first  appear ;  but  several  instances  are  re- 


EFFECTS   OF    EXTERNAL    APPIJCATION.  647 

conlod  ill  wliicli  the  symptoms  were  delayed  niiieli  beyond  the  orili- 
nary  period,  even  under  conditions  apparently  the  most  favorable  for 
their  development. 

It  need  hanlly  be  remarked  that  the  effects  of  strychnine  may  be 
nnuh  modified  by  the  ])resenoe  of  another  poison.  A  case  of  tills 
kind,  in  which  tiu'ee  grains  of  strychnine  and  one  drachm  of  opium 
were  taken  and  no  serious  symptoms  appeared  for  nearly  twelve 
hours,  has  already  been  mentioned  (Introduction,  39).  The  fol- 
lowing somewhat  similar  case  may  also  be  cited.  A  yoimg  drug- 
gist, with  suicidal  intent,  swallowed,  at  half-past  eight  o'clock  in  the 
evening,  between  eight  and  ten  grains  of  nitrate  of  strychnine  in  an 
ounce  of  bitter-almond  water.  A  little  later,  he  took  an  additional 
dose  of  twelve  grains  of  strychnine.  Feeling  nothing  peculiar,  he 
took  at  nine  o'clock  ten  grains  of  acetate  of  morphine  dissolved  in 
an  ounce  of  bitter-almond  water,  and  then  lay  down  in  bed.  Ten 
minutes  later,  to  hasten  his  death,  he  poured  some  chloroform  on  his 
pillow.  Partial  insensibility  now  manifested  itself,  and  continued 
for  about  an  hour  and  a  half,  when  he  was  seized  with  violent 
cramps  and  cessation  of  respiration,  but  without  pain.  Loss  of  con- 
sciousness then  supervened,  but  he  soon  revived,  and  had  another 
attack  of  convulsions.  Emetics  and  tannic  acid  were  now  admin- 
istered ;  and  iu  two  days  afterward  no  trace  of  the  poisoning  re- 
mained. {Amer.  Jour.  Med.  Sci.,  Jan.  1863,  259.)  Recovery  in 
this  case  has  been  ascribed  to  the  fact  that  the  patient,  before  taking 
the  poison,  had  partaken  freely  of  a  soup  made  with  flour  and  a 
species  of  cranberries.  These  latter  contain  tannin,  an  agent  which 
is  said  to  neutralize  strychnine ;  and  the  farinaceous  matters,  by 
enveloping  the  poison,  may  have  prevented  its  absorption.  In 
another  case,  a  young  woman  having  taken  about  one  grain  and  a 
half  of  strychnine,  and  immediately  afterward  two  ounces  of  lauda- 
num, symptoms  of  opium  poisoning  appeared  in  four  hours;  but 
the  effects  of  the  strychnine  did  not  manifest  themselves  until  about 
eight  houis  after  the  poison  had  been  taken.  Under  treatment,  the 
woman  entirely  recovered.     {3Iedical  Times,  Dec.  1882,  175.) 

The  extei^al  application  of  strychnine  may  be  attended  with 
serious  and  even  fiatal  consequences.  In  a  case  related  by  Dr. 
Schuler,  something  less  than  the  twelfth  of  a  grain  of  pure  strych- 
nine was  introduced  into  the  corner  of  the  eye  of  a  man  affected 
with  amaurosis.     In  less  than  three  or  four  minutes  the  patient's 


548  STRYCHNINE. 

face  became  livid,  and  he  was  seized  with  spastic  yawnings  and 
vertigo.  These  symptoms  increased,  and  loss  of  speech  and  pulse, 
with  convulsive  respiration  and  violent  tetanic  shocks,  ensued. 
Death  seemed  inevitable,  but,  under  the  action  of  remedies,  all  the 
symptoms  passed  off  in  less  than  half  an  hour.  [Amer.  Jour.  Med. 
Sci.,  Oct.  1861,  573.) 

It  was  formerly  believed  that  strychnine,  when  given  in  fre- 
quently repeated  small  doses,  never  accumulates  in  the  system ;  but 
this  result  has  occasionally  been  observed.  Thus,  Dr.  Dutgher  re- 
lates a  case  in  which  he  administered  to  a  middle-aged  woman, 
affected  with  partial  paralysis  of  the  muscles  of  deglutition,  the  fifth 
of  a  grain  of  strychnine  daily,  in  divided  doses,  for  nine  days,  with- 
out any  effect  other  than  a  gradual  improvement  of  the  paralytic 
condition.  But  on  the  morning  of  the  tenth  day  the  patient  was 
seized  with  pretty  severe  tetanic  spasms,  which  continued,  at  inter- 
vals of  about  twenty  minutes,  for  several  hours,  when  they  ceased, 
and  the  patient  recovered  without  any  vestige  of  the  paralysis  re- 
maining. [Med.  and  Surg.  Reporter,  Philadelphia,  July,  1865,  2.) 
It  will  be  observed  that  the  entire  quantity  of  strychnine  taken  in 
this  case  did  not  exceed  two  grains. 

A  fatal  case  apparently  of  this  kind  was  communicated,  by  Mr. 
Cooper,  to  the  late  Dr.  Pereira.  [Mat.  Med.,  ii.  548.)  A  Swede, 
affected  with  general  paralysis,  was  given  one-eighth  of  a  grain  of 
strychnine  three  times  a  day  for  several  weeks.  The  dose  was  then 
increased  to  one-quarter  of  a  grain,  and  afterward  to  half  a  grain, 
with  the  same  frequency,  for  many  days,  without  any  marked  effect. 
But  one  morning  the  patient  was  found  insensible,  the  face  and  chest 
of  a  deep  purple  color ;  the  respiration  had  ceased,  and  the  whole 
body  was  in  a  state  of  tetanic  spasm  and  rigid.  The  symptoms 
passed  off,  and  the  man  became  apparently  sensible ;  but  another 
paroxysm  soon  occurred,  and  proved  rapidly  fatal. 

In  regard  to  the  dia^gnosis  of  strychnine  poisoning,  the  only  dis- 
ease with  which  its  symptoms  could  be  confounded  is  tetanus  arising 
from  ordinary  causes.  But  there  is  rarely  any  difficulty  in  deter- 
mining the  true  nature  of  the  case.  Thus,  in  poisoning  the  symp- 
toms appear  suddenly  in  a  violent  form ;  the  muscles  of  the  hands 
are  the  first,  and  those  of  the  jaws  the  last,  to  become  affected ;  there 
is  usually  a  complete  intermission  in  the  symptoms  ;  and  they  rapidly 
run  their  course,  rarely  lasting  over  a  few  hours  at  most.     On  the 


PERIOD   WHEN   FATAL.  549 

other  hand,  in  the  disease  the  symptoms  are  slowly  developed;  the 
muscles  of  the  jaws  are  the  first,  and  those  of  the  hands  the  last,  to 
become  involved ;  there  is  at  most  only  a  remission  of  the  rif:;id 
state  of  the  system;  and  death  rarely  occurs  within  twenty-four 
hours,  the  case  often  being  protracted  for  several  days.  Dr.  Ham- 
mond states  that  in  ordinary  tetanus,  epigastric  pain,  due  to  spasm 
of  the  diaphragm,  is  an  early  and  prominent  symptom  ;  whereas  in 
strychnine  poisoning  this  symptom  is  absent.  {Diseases  of  (he 
Nenmis  System,  555.)  Pain  in  the  epigastrium  has,  however,  been 
present  in  strychnine  poisoning;  and  also  in  several  instances  of 
poisoning  by  nux  vomica. 

Period  when  Fatal. — A  case  is  recorded  in  which  a  young  man, 
through  the  ignorance  of  a  druggist,  took  one  grain  and  two-thirds 
of  strychnine,  with  the  same  quantity  of  nux  vomica,  and  "  he  very 
soon  afterward  complained  of  some  extraordinary  sensations,  and 
almost  immediately  expired."  {Amer.  Jour.  Med.  Sci.,  April,  1854, 
537.)  In  a  case  privately  communicated  to  Dr.  Taylor,  ten  grains 
of  strychnine,  given  in  mistake  for  sulphate  of  quinine,  proved  fatal 
in  ten  minutes.  {On  Poisons,  781.)  In  the  case  of  Dr.  Warner, 
already  mentioned,  death  occurred  in  about  eighteen  minutes  after 
the  poison  had*been  taken.  Dr.  Geoghegan,  of  Dublin,  relates  an 
instance  in  which  five  grains  proved  fatal  in  from  twenty  to  twenty- 
five  minutes;  and  in  Dr.  Barker's  case,  already  cited,  six  grains 
caused  death  in  about  thirty  minutes.  In  a  case  described  by  Dr. 
Theinhart,  in  which  nearly  thirty  grains  of  the  poison  were  taken, 
violent  symptoms  appeared  in  about  fifteen  minutes,  and,  after  four 
convulsive  paroxysms,  death  occurred  in  half  an  hour.  {Amer.  Jour. 
Med.  Sci.,  Jan.  1848,  303.)  Dr.  Gray  mentions  an  instance  in  which 
death. occurred  in  five  minutes  after  the  invasion  of  the  symptoms. 

On  the  other  hand,  in  the  well-known  case  of  Cook,  poisoned 
by  Palmer,  the  symptoms  were  delayed  for  nearly  an  hour,  and  death 
occurred  in  about  an  hour  and  a  quarter  after  the  poison  had  been 
taken.  We  have  elsewhere  recorded  a  case  in  which  a  man  named 
Freet  took  an  unknown  quantity  of  the  poison,  and  violent  symp- 
toms appeared  Jn  about  half  an  hour,  but  death  did  not  take  place 
until  an  hour  later.  {Ohio  Medical  and  Surgical  Journal,  March, 
1864,  95.)  In  a  case  described  by  Dr.  Steiner, — that  of  Dr.  Gardi- 
ner, of  Washington  City, — death  did  not  occur  until  after  the  lapse 
of  three  hours  and  a  half,  although  violent  symptoms  were  present 


550  STJRYCHNINE. 

shortly  after  the  poison  had  been  taken.  {Report  on  Strychnia,  Phila- 
delphia, 1856.)  A  still  more  protracted  case  has  been  reported  by 
Dr.  Paley,  in  which  death  did  not  occur  until  after  the  lapse  of  about 
tive  hours.  (Med.-Chir.  Rev.,  Oct.  1860,  382.)  Dr.  J.  J.  Eeese, 
of  Philadelphia,  reports  the  case  of  a  woman,  in  which  death  was  de- 
layed for  from  five  to  six  hours.  {Amer.  Jour.  Med.  Sd.,  Oct.  1861, 
409.)  At  a  subsequent  trial  of  this  case,  as  personally  informed  by 
Wm.  H.  Miller,  Esq.,  who  was  engaged  in  the  trial,  it  fully  appeared 
in  evidence  that  the  deceased  had  taken  from  five  to  six  grains  of  the 
poison,  and  death  was  delayed  something  over  six  hours. 

The  most  protracted  case  in  this  respect  yet  reported  is  related 
by  M]\I.  Tardieu  and  Roussin  [Ann.  d'Hyg.,  July,  1870,  128j,  in 
which  an  abandoned  young  woman  survived  the  effects  of  a  large 
dose  of  the  poison  for  a  period  of  about  eighteen  hours  after  the  symp- 
toms first  appeared,  the  woman  being  intoxicated  when  first  seen. 
On  inspection,  eleven  grains  (.71  gramme)  of  solid  strychnine  were 
found  adherent  to  the  mucous  membrane  of  the  stomach  ;  about  three 
grains  of  the  absorbed  poison  were  extracted  from  the  tissues. 

Fatal  Quantity. — There  seems  to  be  much  difference  in  the  sus- 
ceptibility of  different  persons  to  the  action  of  strychnine.  Dr.  G.  B. 
Wood  mentions  an  instance  in  which  a  lady  was  thrown  into  violent 
and  even  alarming  spasms,  almost  threatening  suffocation,  by  one- 
twelfth  of  a  grain  of  strychnine.  [Therapeutics,  i.  834.)  In  a  case 
related  by  M.  Duriau,  one-sixth  of  a  grain  taken  by  a  woman,  aged 
twenty-eight  years,  produced  in  ten  minutes  afterward  violent* tetanic 
convulsions,  in  which  the  whole  body  became  rigid ;  similar  attacks 
ensued  at  intervals  of  a  few  minutes  between  each,  and  these  were 
succeeded  by  a  sense  of  burning  in  the  epigastrium  and.  pharynx,  and 
great  irritability  of  the  stomach,  which  lasted  for  not  less  than  six 
weeks.  [Amer.  Jour.  Med.  Sci.,  Oct.  1862,  562.)  In  the  case  of  Dr. 
Warner,  it  is  believed  that  not  over  half  a  grain  of  sulphate  of  strych- 
nine had  been  taken.  This  seems  to  be  the  smallest  quantity  that 
has  yet  proved  fatal  to  an  adult.  In  a  case  reported  by  Dr.  Ogston, 
three-quarters  of  a  grain  destroyed  the  life  of  a  man  in  three-cj^uarters 
of  an  hour;  and  Dr.  Watson  relates  an  instance  in  which  a  similar 
quantity  caused  the  death  of  a  girl,  aged  twelve  years,  in  about  one 
hour.  Mr.  Bennett  describes  a  case  in  which  one  grain  and  a  half 
caused  the  death  of  a  girl,  aged  thirteen  years,  in  two  hours  and  a 
half  {Lancet,  Aug.  1850,  462);  and  Mr.  C.  Bullock  relates  a  case 


FATAr,    (QUANTITY. 


551 


{Amer.  Jour.  Phai^n.,  July,  1870,  309)  in  wlilch  a  similar  quantity 
proved  fatal.  Dr.  Pcreira  {Mat.  Med,  ii.  549)  cites  the  instance  of 
a  ladv  who  died  in  less  than  two  hours  from  the  effects  of  between 
two  and  three  grains  ol'  the  jmison. 

Recovery  has  not  unfrcciucntly  taken  place  after  comparatively 
large  quantities  of  strychnine  had  been  taken.  A  case  of  this  kind 
in  which  five  grains  were  taken,  and  another  in  whi(rh  seven  grains 
were  taken  in  two  doses  of  three  and  a  half  grains  each  at  an  interval 
of  five  hours,  have  already  been  cited.  Wharton  and  Stille  quote 
three  instances  of  recovery  in  each  of  which  four  grains  of  the  poison 
had  been  swallowed  {3fed.  Jur.,  624) ;  and  a  fourth  case  of  this  kind 
is  reported  by  Dr.  Lescher,  of  Illinois,  and  still  another  by  Dr. 
AValler  {MecL  and  Surg.  Reporter,  Philadelphia,  Oct.  1865,  277). 
In  another  instance,  related  by  Dr.  Givens,  a  young  man  swallowed, 
with  suicidal  intent,  two  large  pills  containing  not  less  than  ten  or 
twelve  orains  of  strvchnine.  Violent  tetanic  spasms  soon  ensued, 
and  continued  for  five  hours.  In  seven  iiours  the  spasms  entirely 
subsided,  leaving  the  patient  quite  prostrated,  with  much  distention 
and  tenderness  of  the  epigastrium,  and  stricture  and  soreness  of  the 
throat,  and  of  the  muscular  system  in  general.  These  effects  gradu- 
ally passed  off,  and  in  less  than  a  week  the  patient  >vas  nearly  well. 
Soon  after  the  patient  had  taken  the  poison,  vomiting  occurred,  but 
it  is  not  certainly  known  that  the  pills  were  ejected.  [Med.-Chir. 
Rev.,  April,  1857,  502.) 

In  a  case  reported  by  Dr.  Wilson  [Amer.  Jour.  Med.  ScL,  Jidy, 
1864,  70),  a  young  man,  twenty-two  years  of  age,  recovered  in  about 
fifteen  hours,  although  it  is  believed  that  he  had  taken  forty  grains 
of  strychnine.  There  is,  however,  in  this  instance  niucli  uncer- 
tainty as  to  the  quantity  of  poison  really  taken;  moreover,  there 
seems  to  have  been  very  early  vomiting.  In  a  case  reported  by  Dr. 
Clark,  a  man  laboring  under  delirium  tremens  swallowed  over  twenty 
grains  of  the  poison,  and  eighteen  hours  afterward  he  was  convales- 
cent. {Buffalo  Med.  and  Surg.  Jour.,  Nov.  1866,  135.)  In  this 
case,  also,  there  was  early  vomiting.  After  the  action  of  the  emetics, 
the  patient  was  kept  under  tiie  influence  of  chloroform  for  eight  con- 
secutive hours,  during  which  time  all  attempts  to  suspend  its  use 
were  attended  with  a  recurrence  of  the  convulsions.  In  a  more  re- 
cent case,  a  young  man,  aged  nineteen,  voluntarily  swallowed  over 
thirty  grains  (two  grammes)  of  crystallized  strychnine  at  midnight 


552  STRYCHNINE. 

after  a  full  meal.  When  iirsl  seen,  at  five  o'clock  the  next  morning, 
he  was  found  in  tetanic  convulsions.  Olive-oil,  brandy,  laudanum, 
and  other  remedies  being  employed,  the  patient  was  completely  re- 
stored four  days  after  taking  the  poison.  (New  Remedies,  April, 
1879,  117.)  in  a  case  recently  reported  by  Dr.  W.  T.  Parker, 
Assistant  Surgeon  U.S.A.,  a  colored  soldier,  aged  twenty-three  years, 
fully  recovered  after  having  eaten,  it  is  believed,  about  fifteen  grains 
of  solid  strychnine.     {Medico-Legal  Journal,  Dec.  1884,  375.) 

Treatment. — This  consists  in  the  speedy  administration  of  an 
emetic  or  the  employment  of  the  stomach-pump.  As  an  emetic, 
finely-powdered  mustard  or  zinc  sulphate  may  be  employed.  The 
action  of  the  emetic  should  be  aided  by  the  free  use  of  warm  demul- 
cent drinks.  On  account  of  the  difficulty  of  swallowing,  or  the  rigid 
state  of  the  jaws,  it  is  sometimes  impossible  to  resort  to  the  use  of 
emetics  or  the  stomach-pump.  Of  the  various  remedies  that  have 
been  proposed,  the  internal  administration  of  chloroform,  as  first 
employed  by  Dr.  Dresbach,  of  Tiffin,  Ohio,  seems  to  be  much  the 
most  efficient.  In  a  case  in  which  a  man  had  by  mistake  swallowed 
a  solution  of  three  grains  of  strychnine,  and  most  violent  symj)toms 
were  present  in  twenty  minutes,  Dr.  Dresbach  administered  two 
drachms  of  chloroform,  and  there  was  complete  relief  in  less  than 
twenty  minutes  afterward.  {Amer.  Jour.  Med.  Sci.,  April,  1850, 
546.)  In  another  instance,  related  by  Dr.  J.  E..  Smith,  the  inhala- 
tion of  the  vapor  of  chloroform  was  attended  with  similar  results. 
[Ibid.,  July,  1860,  278.)  Another  case  of  this  kind,  in  which  four 
grains  of  strychnine  had  been  taken,  is  reported  by  Dr.  Bly.  {Neio 
York  Jour,  of  Med.,  Nov.  1859,  422.)  So,  also,  in  a  case  communi- 
cated to  Dr.  G.  B.  Wood,  in  which  a  robust  young  man  had  taken 
four  grains  of  the  poison  and  was  seized  with  the  most  violent  tetanic 
spasms,  complete  recovery  took  place  under  the  use  of  chloroform, 
given  both  internally  and  by  inhalation.  (Z7.  >S'.  Dispensatory,  1865, 
1357.)  In  this  case  it  is  stated  that  it  was  necessary  to  keep  the 
patient  under  the  influence  of  the  chloroform  for  thirteen  consecutive 
hours,  during  which  two  pounds  were  consumed  by  inhalation.  Two 
drops  were  given  every  five  minutes  by  the  stomach,  when  the  mouth 
could  be  opened.  In  a  case  related  by  Dr.  G.  W.  Copeland,  a  man 
knowingly  took  five  grains  of  strychnine,  and  was  fully  restored 
under  the  inhalation  of  chloroform  continued  for  eleven  hours.  At 
no  time  in  this  instance  was  there  vomiting,  although  twenty  grains 


ANTIDOTES. 


553 


of  zinc  siilplKitc  liad  been  given.     {Lancet  and  Observe)-,  Cincinnati, 
Jan.  1874,  41.) 

As  a  choniical  antidote,  tannic  acid  lias  been  strongly  advised  ; 
and  Dr.  Kurzak,  of  N'ienna,  luis  performed  a  series  of  experiments 
upon  inferior  animals,  iVoin  wliidi  it  wonld  apiu'ar  that  this  substance, 
if  administered  early,  has  the  property  of  suspending  the  action  of 
tlie  poison.  He  states  that  about  twenty-five  parts  of  tannin  are 
required  for  one  part  of  strychnine.  In  the  absence  of  tannin  in 
its  pure  form,  a  strong  infusion  of  powdered  gall-nuts  or  of  green 
tea  might  be  exhibited.  {North  American  Med.-Chir.  Rev.,  July, 
I860.)"  The  utility  of  this  acid  is  supposed  to  depend  upon  its 
uniting  with  the  poison  to  form  tannate  of  strychnine,  which  is  in- 
soluble in  water,  but  readily  soluble  in  acids.  M.  Bouchardat  recom- 
mends, as  an  antidote,  a  solution  of  iodine  in  potassium  iodide.  The 
precipitate  produced  by  this  mixture  is  somewhat  less  soluble  in 
diluted  acids  than  that  occasioned  by  tannic  acid.  It  need  hardly  be 
remarked  that  neither  of  these  substances  should  be  relied  on  to  the 
exclusion  of  emetics  or  the  stomach-pump.  Among  the  other  sub- 
stances that  have  been  recommended  as  antidotes  may  be  mentioned 
chlorine,  bromine,  animal  charcoal,  camphor,  and  lard,  or  fat.  A 
case  in  which  four  grains  of  strychnine  had  been  taken  and  recovery 
took  place  under  the  use  of  emetics  and  camphor,  is  related  by  Dr. 
Rochester.     {Buffalo  Medical  Journal,  March,  1856.) 

Upon  physiological  grounds,  Prof.  Houghton  was  led  to  believe 
that  strychnine  and  nicotine  (the  active  principle  of  tobacco)  might 
be  mutually  antidotal,  and  he  cites  a  few  experiments  on  frogs  in 
support  of  this  view.  And  Dr.  O'Reilly,  of  St.  Louis,  has  related 
an  instance  in  which,  acting  upon  this  suggestion,  he  adminis- 
tered, in  divided  doses,  an  infusion  of  an  ounce  and  a  quarter  of 
tobacco  to  a  man  who  had  taken  six  grains  of  strychnine,  and  the 
patient  recovered.  {3Ied.-Chir.  Review,  Oct.  1859,  387.)  Since, 
however,  in  this  instance,  previous  to  the  administration  of  the 
alleged  antidote,  an  emetic  had  been  given  and  operated,  it  is  not 
certain  that  the  recovery  was  in  any  way  due  to  the  effects  of  the 
tobacco.  Another  instance  in  which  an  infusion  of  tobacco  was 
employed,  and  the  patient  recovered,  has  been  reported  by  Dr. 
Chevers,  of  Calcutta.  {Ibid.,  Jan.  1867,  243.)  But  in  this  instance, 
also,  there  seems  to  have  been  vomiting  prior  to  the  administration 
<if  the  tobacco;  moreover,  it  appears  that  the  patient,  a  girl  aged 


554  STEYCHNIJSTE. 

eleven  years,  had  swallowed  only  a  comparatively  small  quantity, 
perhaps  very  much  less  than  one  grain,  of  the  poison. 

For  the  purpose  of  testing  the  antidotal  properties  of  nicotine, 
we  administered  to  each  of  thirteen  healthy  cats  half  a  grain  of 
pure  strychnine,  the  poison  being  passed  in  solution  into  the  stomach 
by  means  of  a  stomach-tube.  In  some  instances,  as  soon  as  symp- 
toms of  the  poison  appeared,  an  infusion  of  twenty  grains  of  tobacco- 
leaves  was  administered,  in  the  same  manner  as  the  poison ;  whilst 
in  others,  the  tobacco-infusion  was  given  along  with  the  strychnine, 
the  two  solutions  being  thoroughly  mixed.  In  some  few  cases  the 
dose  of  tobacco  was  repeated.  As  the  result  of  these  experiments  : 
one  of  the  animals  which  had  taken  the  mixed  solutions  imme- 
diately fell  prostrate,  breathed  with  difficulty,  in  three  minutes 
voided  urine,  in  eight  minutes  vomited  a  frothy  mucus,  and  in 
ten  minutes  was  able  to  run,  with,  however,  a  stiif  gait ;  after  an 
hour  the  animal  appeared  perfectly  w^ell,  except  a  slight  stiffness 
in  walking.  With  this  single  exception,  all  the  animals  died, 
and  in  most  instances  within  the  usual  period ;  one  of  them,  how- 
ever, that  had  taken  the  mixed  solutions,  manifested  no  symptom 
whatever  for  thirty-five  minutes.  In  some  instances  the  strych- 
nine symptoms  appeared  to  be  not  in  the  least  affected  by  the 
tobacco;  but  in  others  they  were  of  a  compound  nature.  Several 
of  the  animals  vomited.  Before  performing  these  experiments,  it 
was  ascertained  that  an  infusion  of  twenty  grains  of  tobacco,  given 
alone,  would  produce  serious  symptoms ;  but  in  no  instance,  in  six 
experiments,  did  it  cause  death. 

From  one  hundred  and  forty-three  experiments  made  by  Dr.  F. 
L.  Haynes,  upon  rats,  cats,  rabbits,  and  dogs,  with  strychnine  and 
tobacco  or  nicotine,  he  concluded  that  these  substances  were  in  no 
degree  antagonistic.     (Proc.  Ame7\  Philos.  Soc,  1877,  596.) 

M.  Liebreich  strongly  advised  chloral  as  antidotal  to  strychnine, 
and  a  number  of  instances  are  reported  in  which  this  substance  was 
used  with  advantage.  Dr.  G.  Gray  reports  a  case  in  which  twenty 
grains  of  strychnine  had  been  taken,  and  under  the  administration 
of  two  drachms  of  chloral  hydrate  the  patient  entirely  recovered. 
[Amer.  Jour.  Pharm.,  Sept.  1880,  475.)  More  recently.  Prof.  V. 
Cervello  has  proposed,  for  this  purpose,  jjaraldehycle,  he  having 
found  in  a  series  of  experiments  that  this  agent  completely  antag- 
onized enormous  doses  of  strychnine.     (Medical  News,  March,  1884, 


PATHOLOGICAL    EFFECTS. 


555 


361.)     So,  also,   (imyl  nitrite  has   been   advised   as   a   pliysiological 

antidote. 

Post-mortem  Appearances. — The  most  constant  appearances 
in  death  iVoin  strychnine  arc  engorgement  of  tlie  hings,  and  fulness 
of  the  hhiod-vesseis  of  the  brain  and  its  membranes,  with  a  fluid 
condition  and  dark  color  of  tiie  blood.  The  heart  is  generally 
empty  and  tlaceid.  In  some  instances  there  is  more  or  leas  redness 
of  the  raucous  membrane  of  the  stomach.  Congestion  of  the  liver, 
spleen,  and  kidneys  has  also  been  observed.  The  body  usually  pre- 
sents a  more  or  less  livid  appearance.  One  of  the  most  striking 
characters  in  death  from  this  substance  is  the  rigid  condition  assumed 
by  the  body  soon  after  death.  In  this  state,  the  joints  are  fixed,  the 
abdomen  hard  and  tense,  the  legs  extended,  the  feet  arched,  the  fingers 
firmly  closed,  and  the  head  thrown  back.  In  a  case  reported  by 
Dr.  Paley,  of  Peterborough,  death  took  place  during  a  paroxysm, 
and  the  tetanic  rigidity  continued  for  some  time  afterward,  the  arms 
being  crossed  and  forcibly  bent  over  the  chest,  the  hands  rigidly 
closed,  and  the  legs  perfectly  stiff;  but  in  twenty-three  hours  there 
was  no  unusual  rigidity  about  the  limbs.  [Med.-Chir.  Rev.,  Oct. 
1860,  384.)  In  all  the  animals  we  have  killed  with  this  poison, 
the  bodies  were  flaccid  at  the  time  of  death,  but  the}^  soon  became 
rigid.  A  like  result  was  observed  by  Prof.  Ranke  in  seventeen 
dogs  killed  by  strychnine:  the  time  of  the  first  appearance  of  rigid- 
ity varied  from  twenty-one  to  ninety-seven  minutes  after  death. 
{Ann.  cVHyg.,  April,  1881,  387.) 

In  the  case  reported  by  Dr.  Theinhart,  in  which  death  took  place 
in  half  an  hour,  the  tongue,  gums,  and  lips,  as  also  the  fingers  and 
toes,  were  of  a  violet  color ;  the  fingers  were  closed,  and  the  toes 
drawn  in  ;  and  the  whole  body  was  as  rigid  as  a  stick  of  wood,  and 
slightly  bent  upon  itself.  In  a  case  in  which  a  woman  seems  to  have 
died  almost  instantaneously  from  the  effects  of  strychnine,  the  inspec- 
tion showed  great  rigidity  of  the  muscles,  the  stomach  contracted  in 
the  form  of  a  dumb-bell,  and  the  left  heart  most  firmly  contracted 
and  empty,  the  right  being  also  nearly  empty.  [Med.-Chir.  Rev., 
Oct.  1869,  552.)  In  Dr.  Blumhardt's  case,  in  which  forty  grains 
of  strvchnine  had  been  taken  and  death  occurred  in  an  hour  and  a 
half,  twenty-four  hours  after  death  the  skin  was  found  of  a  dark 
color,  and  the  body  excessively  rigid.  On  opening  the  vertebral 
canal,  a  large  quantity  of  thick  fluid  blood  escaped.     Tlie  plexuses 


556  STRYCHNINE. 

of  the  spinal  veins  and  the  pia  mater  were  highly  congested.  The 
upper  part  of  the  spinal  marrow  was  exceedingly  soft,  but  the  lower 
portion  hard.  The  substance  of  the  brain  was  slightly  congested, 
but  the  membranes  were  heajthy.  The  stomach  was  nearly  normal, 
and  contained  a  slimy  mucus. 

In  the  case  of  Freet,  already  mentioned,  forty  hours  after  death, 
the  skin  was  livid,  the  body  rigid,  the  hands  clinched,  and  the  toes 
drawn  upwards.  The  lower  extremities  were  stiiF,  but  the  arms 
relaxed.  The  pyloric  end  of  the  stomach  was  somewhat  reddened  ; 
and  the  liver  and  lungs  were  gorged  with  dark  liquid  blood.  The 
blood  throughout  the  body  was  of  a  dark  color  and  fluid.  The 
brain  was  healthy,  but  its  vessels  were  nearly  destitute  of  blood. 
The  kidneys  and  bladder  were  normal.  In  Dr.  Steiner's  case, 
eighteen  hours  after  death,  the  body  was  extremely  rigid,  and  the 
face,  neck,  and  back  were  livid.  The  scalp  and  membranes  of  the 
brain  were  highly  congested  with  dark  liquid  blood ;  but  the  sub- 
stance of  the  brain  and  spinal  marrow  presented  nothing  abnormal. 
The  heart  was  small,  contracted,  and  contained  no  blood.  The  liver, 
spleen,  and  pancreas  were  natural,  but  the  kidneys  were  highly  con- 
gested. In  the  case  described  by  Dr.  Reese,  six  weeks  after  death, 
the  body  was  found  very  rigid,  and  in  a  good  state  of  preservation; 
the  heart  was  healthy,  and  contained  a  considerable  quantity  of  blood. 
In  Dr.  Paley's  case,  in  which  life  was  prolonged  for  about  five  hours, 
the  only  abnormal  appearances  found  in  the  body,  twenty-three  hours 
after  death,  were  slight  traces  of  inflammation  of  the  lining  mem- 
branes of  the  stomach  and  ileum,  and  a  generally  congested  state  of 
the  thoracic  and  abdominal  organs ;  the  heart  was  nearly  empty,  and 
the  blood  of  a  dark  color  and  fluid. 

The  following  case,  in  which  a  large  quantity  of  the  poison  had 
been  taken  and  proved  rapidly  fatal,  is  reported  by  Dr.  Buck.  {Amer. 
Med.  Times,  Oct.  1863,  205.)  Four  hours  after  death,  the  body  was 
still  warm,  the  face  livid,  eyes  open,  pupils  natural,  jaws  firmly 
closed,  lips  slightly  parted,  and  frothy  matter  \vas  escaping  from  the 
mouth.  The  muscles  of  the  neck  were  relaxed,  the  arms  rigid,  and 
the  elbows  fixed  at  right  angles,  with  the  forearms  across  the  chest ; 
the  fingers  were  semi-flexed,  and,  when  forcibly  extended,  would 
fly  back ;  the  same  was  true  of  the  elbow.  The  legs  were  rigidly 
extended,  the  feet  arched,  and  the  great  toes  drawn  in.  In  twenty- 
four  hours  after  death,  the  neck,  back,  left  arm,  right  shoulder,  and 


GENERAL   CHEMICAL    NATURE.  557 

hip-joint«  were  rel:ixed  ;  but  the  other  parts  of"  tlie  body  wero  in 
the  same  condition  as  l)efore.  On  openinoj  the  cranium,  a  large 
quantity  of  blood  escaped  from  that  cavity.  The  membranes  of 
the  brain  were  congested,  but  the  brain  and  spinal  marrow  were 
healthy.  The  lungs,  lining  membrane  of  the  trachea,  and  muscles 
in  front  of  the  neck  were  congested.  The  heart  was  firmly  con- 
tracted, the  ventricles  empty,  and  only  a  very  little  blood  in  the 
auricles.  The  mucous  membrane  of  the  cardiac  portion  of  the 
stomach  was  congested ;  all  the  other  organs  of  the  abdomen  were 
heahliy.  A  chemical  examination  of  the  contents  of  the  stomach, 
by  Dr.  A.  A.  Hayes,  of  Boston,  revealed  the  presence  of  a  large 
quantity  of  strychnine. 

Chemical  Properties. 

General  Chemical  Nature. — In  its  pure  state,  strychnine 
crystallizes  in  the  form  of  colorless,  transparent  octahedra  or  in 
lengthened  prisms.  When  precipitated  from  complex  organic  solu- 
tions, it  often  appears  in  the  form  of  minute  granules.  As  found  in 
the  shops,  it  is  sometimes  in  the  form  of  a  white  or  dull-white  amor- 
phous powder,  at  other  times  in  the  form  of  well-defined  crystals. 
Strychnine  has  a  most  intensely  bitter  taste,  but  it  -is  destitute  of 
odor.  It  is  not  decomposed  either  by  the  cold  concentrated  mineral 
acids  or  the  caustic  alkalies.  When  heated,  it  fuses  to  a  brownish 
liquid,  then  undergoes  decomposition,  with  the  evolution  of  dense, 
white  fumes ;  when  heated  in  the  flame  of  a  spirit-lamp,  it  takes  fire 
and  burns  with  a  yellowish  smoky  flame.  If  the  heat  be  gradually 
increased,  strychnine  may  be  sublimed  unchanged.  According  to 
Prof.  Guy,  it  begins  to  vaporize  at  174°  C.  (345°  F.),  and  fuses  at 
221°  C.  (430°  F.) 

Strychnine  has  strong  basic  properties,  and  readily  unites  with 
acids  to  form  salts,  most  of  which  are  easily  crystallizable.  The 
salts  of  strychnine,  except  when  containing  a  colored  acid,  are  color- 
less ;  they  have  the  intensely  bitter  taste  of  the  pure  alkaloid,  and  are 
equally  poisonous.  The  neutral  sulphate,  2C21H22N2O2 ;  H2SO4,  crys- 
tallizes in  the  form  of  transparent,  colorless,  four-sided  prisms,  which 
are  usually  said  to  contain  seven  molecules  of  water  of  crystallization  : 
later  researches,  however,  indicate  that  the  crystals  contain  sometimes 
five,  and  at  other  times  six,  molecules  of  water,  but  never  seven,  as 
assigned  by  Regnault.     On  exposure  to  the  air,  the  crystals  become 


558  STRYCHXIXE. 

opaque  from  loss  of  water  of  crystallization.  The  acid  sulphate, 
when  crystallized,  has  the  composition  C2iH22X202,H2SO^,2H20. 

The  hydrochloride,  or  chloride,  C2iH22j!^202,HCl,  forms  slender 
crvstalline  needles,  which,  according  to  Gerhardt,  contain  one  mole- 
cule of  water.  The  nitrate  and  the  acetate  appear  in  the  form  of 
beautiful  silky  needles;  the  latter  of  these  salts,  however,  crystallizes 
with  difficulty. 

Solubility.  1.  In  Wafer. — When  excess  of  pure  powdered 
strychnine  is  digested  at  the  ordinary  temperature  for  twenty-four 
hours,  with  frequent  agitation  in  distilled  water,  the  solution  then 
filtered,  and  the  filtrate  evaporated  to  dryness  at  a  moderate  tempera- 
ture, it  leaves  a  crystalline  residue  indicating  that  one  part  of  the 
alkaloid  had  dissolved  in  8333  parts  of  the  liquid.  It  is  usually 
stated  that  strychnine  dissolves  in  6667  parts  of  water  at  the  ordi- 
nary temperature ;  but  the  above  is  the  mean  result  of  several  very 
closely  accordant  experiments.  Its  solubility  is  much  increased  by 
a  moderate  heat,  and  much  of  the  excess  long  remains  in  solution. 

2.  In  Ether. — Excess  of  the  finely-powdered  alkaloid  was  digested 
at  the  ordinary  temperature  for  twenty-four  hours  in  absolute  ether, 
and  the  mean  of  several  experiments  indicated  that  one  part  dissolved 
in  about  1400  parts  of  the  liquid.  It  is  somewhat  more  soluble  in 
ordinary  ether.  One  part  of  the  pure  alkaloid  dissolved  in  1050 
parts  of  commercial  ether  of  specific  gravity  0.733. 

3.  Chloroform  readily  takes  up  one  part  of  the  pure  alkaloid  in 
eight  parts  of  the  menstruum. 

4.  Absolute  alcohol,  when  kept  in  contact  at  the  ordinary  tem- 
perature with  excess  of  the  alkaloid,  with  frequent  agitation,  for  four 
hours,  takes  up  one  part  in  207  parts  of  the  liquid.  Under  similar 
conditions,  one  part  of  the  alkaloid  will  dissolve  in  about  400  parts 
of  common  ichishey. 

5.  Amyl  alcohol,  when  agitated  for  a  few  minutes  with  excess 
of  the  alkaloid  at  the  ordinary  temperature,  dissolves  one  part  in 
122  parts  of  the  menstruum. 

6.  Benzene,  or  benzole,  of  specific  gravity  0.878,  when  frequently 
agitated  for  some  hours  with  excess  of  finely-powdered  strychnine, 
dissolved  one  part  of  the  alkaloid  in  140  parts  of  the  fluid.  On 
spontaneous  evaporation,  a  benzene  solution  of  strychnine  leaves  the 
alkaloid  in  the  form  of  large,  brilliant,  octahedral  crystals. 

7.  Petroleum- ether,  of  specific  gravity  0.625,  under  like  conditions, 


SPECIAL  CHEMICAL   PROPERTIES.  559 

dissolved  onlv  one   part  of  stryclmiiic  in  al)<)iit   12,500  parts  of  the 
liquid. 

From  till'  foroi2;()inj;  facts,  it  is  ohvions  that,  other  things  being 
ecjiial,  strychnine  is  niucli  more  completely  extracted  from  its  aqueous 
solution  or  mixture  by  chloroform  than  by  cilier ;  however,  tlic  latter 
liquid  will  usually  answer  very  well  for  the  recovery  of  the  poison. 
The  use  of  chloroform  for  the  extraction  of  the  alkaloid  from  com- 
plex organic  mixtures  has  been  objected  to,  on  the  ground  that  it 
acts  more  solvently  than  ether  upon  foreign  matters;  but  we  have 
not  found  this  objection  to  hold  in  ordinary  practice.  Strychnine  is 
insoluble  in  the  fixed  caustic  alkalies,  and  only  very  sparingly  soluble 
in  ammonia. 

Most  of  the  salts  of  strychnine  are  readily  soluble  in  water  and 
in  alcohol,  they  being  more  freely  soluble  in  the  latter  liquid  than 
the  pure  alkaloid.  They  are  also  soluble  to  an  appreciable  extent  in 
ether.  Thus,  we  find  that  the  acetate  dissolves  in  about  10,000  times 
its  weight  of  this  liquid.  The  insoluble  salts  of  the  alkaloid  are 
readily  soluble  in  the  presence  of  a  free  acid,  even,  with  very  few 
exceptions,  of  acetic  acid. 

Special  Chemical  Peoperties. — Concentrated  sulphuric  acid 
dissolves  strychnine,  as  well  as  its  colorless  salts,  to  a  colorless  solu- 
tion, which,  upon  the  addition  of  a  crystal  of  potassium  dichroraate, 
rapidlv  passes  through  a  highly  characteristic  series  of  colors  (see 
post,  COLOR  test),  a  crystal  of  potassium  nitrate  stirred  in  the 
sulphuric  acid  solution  produces  no  visible  change.  Concentrated 
nitric  acid  dissolves  the  alkaloid  and  its  salts  without  change  of  color, 
even  upon  the  addition  of  stannous  chloride:  if  the  strychnine  be 
contaminated  with  brucine,  as  is  frequently  the  case  as  met  with  in 
commerce,  it  strikes  a  red  or  orange-red  color  with  nitric  acid.  So, 
also,  hydrochloric  acid  dissolves  the  pure  alkaloid  to  a  colorless  so- 
lution. When  moistened  with  a  solution  of  potassium  dichromate, 
strychnine  acquires  a  beautiful  golden-yellow  color. 

Pure  solutions  of  strychnine,  and  of  its  salts,  are  colorless  and 
odorless,  and  have  the  bitter  taste  of  the  pure  alkaloid.  Upon  slow- 
evaporation,  they  leave  the  jioison  in  its  crystalline  form.  An 
alcoholic  solution  of  the  free  alkaloid  quickly  restores  the  blue  color 
of  reddened  litmus-paper.  This  reaction  is  also  perceptible  in  a 
saturated  aqueous  solution  of  the  alkaloid. 

The  taste  of  strychnine,  under  certain  conditions,  is  one  of  its 


560  STRYCHNINE. 

most  characteristic  propertieSj  and  it  may  be  recognized  even  in 
highly  diluted  solutions.  Thus,  a  single  grain  of  a  l-50,000th 
pure  aqueous  solution  of  the  alkaloid — equal  to  the  l-50,000th  of  a 
grain  of  strychnine — has  a  quite  perceptible  bitter  taste.  A  similar 
quantity  of  a  l-100,000th  solution  has  a  perceptible  taste,  but  this 
can  hardly  be  said  to  be  bitter.  It  has  been  asserted  that  even  much 
less  quantities  of  the  poison  than  the  last-mentioned  may  thus  be 
indicated;  but  in  our  own  personal  experience  we  have  not  met  with 
a  person  whose  sense  of  taste  extended  beyond  the  quantities  just 
stated.  Moreover,  the  taste  of  these  minute  quantities  is  readily 
disguised  by  the  presence  of  foreign  substances.  In  a  drop  of  a 
l-10,000th  solution  the  taste  is  usually  very  decided  and  well 
marked,  even  in  the  presence  of  a  very  notable  quantity  of  foreign 
matter. 

That  the  taste  is  equally  or  even  more  delicate  for  the  detection 
of  strychnine  in  its  pu7'e  state  than  any  of  the  known  chemical  tests, 
as  has  been  asserted  by  some  writers,  is  certainly  erroneous.  Never- 
theless, this  is  one  of  the  best  corroborative  tests  yet  known,  and  its 
application  should  never  be  omitted.  On  the  other  hand,  it  should 
be  borne  in  mind  that  an  impure  extract  from  a  complex  mixture 
may  have  a  bitter  taste,  due  to  the  presence  of  strychnine,  and  yet 
fail  to  respond  to  the  color-test  for  the  alkaloid,  the  reaction  being 
prevented  by  the  presence  of  foreign  matter.  Should,  under  ordi- 
nary conditions,  a  bitter  taste  not  be  perceived,  it  would  follow  that 
at  most  there  was  only  a  very  minute  quantity  of  the  alkaloid  pres- 
ent. So,  also,  it  must  be  remembered  that  other  substances,  such 
as  quinine,  quassia,  colocynth,  picrotoxin,  and  morphine,  possess  a 
somewhat  similar  bitterness.  Of  the  bitter  substances  mentioned, 
quinine  is  the  only  one  that,  like  strychnine,  would  be  taken  up  to 
any  notable  extent  by  either  chloroform  or  ether,  when  one  or  the 
other  of  these  liquids  was  used  for  the  extraction.  The  fluorescent 
properties  of  acid  solutions  of  quinine  readily  distinguish  it  from 
strychnine. 

In  the  following  investigations  in  regard  to  the  action  of  reagents 
upon  solutions  of  strychnine,  the  alkaloid  was  employed  in  the  form 
of  a  salt,  but  chiefly  as  the  acetate.  The  fractions  employed  indicate 
the  fractional  part  of  a  grain  of  the  anhydrous  alkaloid  in  solution 
in  one  grain  of  pure  water.  The  results,  unless  otherwise  indicated, 
refer  to  the  behavior  of  07ie  grain  of  the  solution. 


THK   CAUSTIC   ALKALIES.  561 

1.    The  Cdivilic  A//:a/ii'.s. 

Tlie  tixcci  caustic  alkalies  and  ammonia  throw  down  tVoin  some- 
what concentrated  solutions  of  salts  of  stryclinine  a  white,  amorphous 
precipitate  of  the  pure  alkaloid,  which  in  a  little  time  assumes  the 
crystalline  form.  From  more  dilute  solutions  the  precipitate  does 
not  appear  until  after  a  little  time,  and  it  then  separates  in  its  crys- 
talline state.  Solutions  still  more  dilute  may  entirely  fail  to  yield 
a  precipitate.  The  precipitate  is  insoluble  in  potassium  and  sodium 
hydrates,  and  only  sparingly  soluble  in  ammonia,  but  it  immedi- 
ately disappears  upon  the  addition  of  almost  any  of  the  diluted  acids. 
When  a  somewhat  strong  solution  of  a  salt  of  the  alkaloid  is  exposed 
to  the  capor  of  ammonia,  it  immediately  becomes  covered  with  a  white 
film,  and  in  a  little  time  changes  to  a  nearly  solid  mass  of  crystals. 

1.  Yhu  grain  of  strychnine,  in  one  grain  of  water,  yields,  with  either 

of  the  reagents,  an  immediate,  copious  precipitate,  which  very 
soon  becomes  converted  into  a  mass  of  crystals  of  one  or  more 
of  the  forms  illustrated  in  Plate  X.,  fig.  1.  If  after  the  ad- 
dition of  the  reagent  the  mixture  be  allowed  to  remain  very 
quiet,  it  yields  very  beautiful  compound  stellate  crystalline 
groups  of  the  form  illustrated  in  the  lower  part  of  the  figure : 
these  forms  are  especially  apt  to  be  produced  if  the  alkaloid 
contains  a  little  brucine. 

2.  YWoi)  grain  :  after  a  few  moments  crystalline  needles  and  groups 

begin  to  appear,  and  in  a  very  little  time  there  is  a  quite  good 
deposit.  If  upon  the  addition  of  the  reagent  the  mixture  be 
stirred  wath  a  glass  rod,  it  almost  immediately  yields  a  very 
good  amorphous  precipitate,  which  very  soon  changes  into  short 
crystalline  needles. 

3.  YoVo"  S^^^^  '  after  a  few  minutes  a  very  satisfactory  crystalline 

precipitate  has  formed.  If  the  mixture  be  stirred,  the  formation 
of  the  precipitate  is  mucii  facilitated,  and  it  is  more  abundant. 

4.  3-^ij-y  grain,  when  treated  with  a  very  small  quantity  of  reagent, 

yields  after  some  minutes,  especially  if  the  mixture  be  stirred, 
a  very  satisfactory  crystalline  precipitate. 
The  alkali  carbonates  produce,  in  solutions  of  salts  of  strych- 
nine, reactions  similar  to  those  of  the  free  alkalies. 

It  need  hardly  be  remarked  that  the  production  of  a  white  crys- 
talline precipitate  by  either  of  the  foregoing  reagents  is  not  in  itself 

36 


562  STRYCHNINE. 

positive  proof  of  the  presence  of  strychnine.  The  crystalline  forms 
of  this  alkaloid,  however,  are  somewhat  peculiar.  The  true  nature 
of  the  precipitate,  even  when  present  only  in  the  most  minute  quan- 
tity, may  be  readily  established  by  means  of  the  test  just  to  be 
mentioned. 

2.   Color  Test. 

This  test,  which  is  the  most  characteristic,  and  at  the  same  time, 
when  applied  to  the  pure  alkaloid,  one  of  the  most  delicate  yet 
known  for  the  detection  of  strychnine,  is  based  upon  the  development 
of  a  series  of  colors  when  a  sulphuric  acid  solution  of  the  alkaloid  is 
treated  with  certain  oxidizing  agents.  Marchand,  in  1843,  was  the 
first  to  point  out  that  when  strychnine  is  dissolved  in  sulphuric 
acid  containing  a  little  nitric  acid,  and  the  mixture  stirred  with  a 
small  quantity  of  peroxide  (dioxide)  of  lead,  the  liquid  immedi- 
ately acquires  a  deep  blue  color,  which  rapidly  changes  to  purple  or 
violet,  then  gradually  to  red,  which  very  slowly  fades. 

This  development  of  colors  is  due  to  the  action  of  the  nascent 
oxygen  evolved  by  the  acids  and  lead  compound  upon  the  strych- 
nine. Any  combination  that  will  eliminate  oxygen  will  produce 
these  results,  provided  the  substance  from  which  it  is  evolved,  or 
some  substance  evolved  along  with  it  from  the  oxidizing  agent,  does 
not  interfere  with  the  action  of  the  nascent  gas.  Mack,  in  1846, 
proposed  the  use  of  sulphuric  acid  and  manganese  dioxide,  and 
about  the  same  time  Otto  suggested  this  acid  and  potassium  dichro- 
raate.  More  recently  it  has  been  proposed  to  substitute  for  these 
metallic  combinations  various  other  substances,  such  as  potassium 
ferricyanide,  chromic  acid,  the  alkaline  iodates,  potassium  permanga- 
nate, and  eerie  oxide.  Most  of  these  substances  were  advanced  under 
the  claim  either  that  they  were  more  delicate  in  their  reaction  or 
else  less  subject  to  interferences  than  those  that  had  previously  been 
proposed  ;  but  a  careful  and  impartial  comparative  examination  shows 
that  at  most  there  is  but  little  difference  between  them  in  regard  to 
delicacy  of  reaction,  and  that  they  are  all  about  equally  affected  by  the 
presence  of  certain  foreign  substances.  Of  these  different  oxidizing 
substances,  we  prefer,  for  this  purpose,  potassium  dichromate:  this 
salt  is  readily  obtained  in  its  pure  crystalline  state.  For  the  detec- 
tion of  the  very  minute  traces  of  the  alkaloid,  it  is  better  to  have 
the  color-developing  agent  in  the  form  of  a  minute  crystal  than  in 
the  state  of  powder.     Manganese  dioxide  and  lead  dioxide  dissolve 


COLOR  TEST.  563 

in  sulplunic  acid  without  change  of  color;  but  potassium  dichro- 
luato,  iJotassium  ferrieyanide,  and  eerie  oxide  impart  a  yellowish, 
while  potassium  permanganate  gives  a  greenish  color  to  the  acid. 
These  colors,  however,  at  most  undergo  but  slow  change,  and  could 
not  possibly  be  confounded  with  the  series  of  colors  produced  by 
strychnine. 

To  apply  this  test,  a  small  quantity  of  the  alkaloid,  or  any  of  its 
salts,  in  the  solid  state,  is  placed  on  a  piece  of  wdiite  porcelain  or  in 
a  watch-glass  over  white  paper,  and  dissolved  in  a  drop  of  pure  con- 
centrated sulphuric  acid,  in  which,  if  pure,  it  dissolves  without  change 
of  color.  A  small  crystal  of  potassium  dichromate,  or  a  small  por- 
tion of  either  of  the  other  color-developing  agents,  is  now  added 
to  the  solution,  and,  wiien  moistened  with  the  acid,  slowly  moved 
around  in  the  liquid  by  means  of  a  pointed  glass  rod,  when,  either 
immediately  or  in  a  few  moments,  the  peculiar  succession  of  colors, 
beginning  with  a  beautiful  blue,  will  manifest  itself  The  blue  color 
quicklv  passes  into  purple,  this  into  violet,  and  this  more  slowly  into 
red,  which  very  slowly  fades.  The  liquid  ultimately  either  acquires 
a  yellow  or  a  greenish  color,  or  becomes  entirely  colorless ;  but  these 
results  are  altogether  independent  of  the  action  of  the  strychnine. 
An  important  point  to  be  observed,  when  applying  the  test  to  a 
suspected  substance,  is  the  non-coloration  by  the  acid  alone. 

As  the  intensity  and  duration  of  the  colors  thus  produced  depend 
very  much  upon  the  amount  of  strychnine  operated  upon,  as  well  as 
the  relative  quantities  of  acid  and  color-developing  agent  employed, 
and  the  physical  state  of  the  latter,  it  is  impossible  to  give  any  de- 
scription that  will  fully  meet  every  case;  yet  whenever  developed 
they  are  so  peculiar  as  to  be  readily  recognized,  even  when  only  the 
merest  trace  of  strychnine  is  present.  With  a  very  minute  quantity 
of  the  alkaloid  the  blue  color  may  continue  only  for  a  moment,  or 
it  may  even  be  entirely  absent,  the  mixture  developing  at  first  a 
purple  or  a  violet  color,  quickly  passing  to  red.  To  obtain  the  best 
results  from  these  minute  quantities,  the  acid  should  be  very  concen- 
trated and  added  in  very  minute  quantity,  and  only  a  very  small 
fragment  of  the  oxidizing  agent  employed. 

Another  method  of  applying  the  test  is  to  place  a  small  drop  of 
sulphuric  acid  by  the  side  of  the  strychnine,  and  then  stir  a  very 
small  crystal  of  potassium  dichromate  in  the  acid  until  it  imparts  a 
slight  yellow   color  to   the   liquid,   when   the   moistened   crystal  is 


564  STRYCHNINE. 

dragged  over  the  strychnine,  by  means  of  a  pointed  glass  rod  ;  or, 
the  colored  acid  may  be  allowed  to  flow  over  the  alkaloid,  by  gently 
inclining  the  dish.  For  the  recognition  of  minute  quantities  of  the 
poison  this  method  is  even  more  delicate  than  that  just  described. 
Since,  however,  as  we  shall  see  hereafter,  in  examining  a  suspected 
deposit  it  is  frequently  important  to  know  the  action  of  the  acid 
alone,  this  method  is  not  always  applicable.  The  test  may  also  be 
applied  to  solutions  of  strychnine,  by  treating  a  drop  of  the  liquid 
with  a  drop  or  two  of  concentrated  sulphuric  acid,  and  stirring  in 
the  cooled  mixture  a  small  quantity  of  the  color-developing  agent. 
This  method,  however,  applies  only  to  somewhat  strong  solutions  of 
the  alkaloid,  and  even  under  these  circumstances  the  results  are  by 
no  means  as  uniform  as  when  the  strychnine  is  in  its  solid  state. 

Delicacy  of  the  test. — In  the  following  examinations  in  regard 
to  the  limit  of  the  reaction  of  this  test,  the  quantities  of  strychnine 
were  obtained  by  evaporating  one  grain  of  a  corresponding  solution 
of  a  salt  of  the  alkaloid  to  dryness  spontaneously.  This  method  of 
evaporation  is  much  preferable  to  that  on  a  water-bath,  since  it  much 
more  frequently  leaves  the  poison  in  its  crystalline  state,  which  is 
better  adapted  to  the  application  of  the  test  than  the  amorphous 
form.  The  results  refer  niore  especially  to  those  produced  by  potas- 
sium dichromate  as  the  oxidizing  agent,  and  are  based  on  very 
frequently  repeated  experiments. 

1.  yi-g-  grain  of  strychnine,  in  the  form  of  acetate,  when  obtained  in 

the  manner  just  described,  forms  a  very  fine  crystalline  deposit, 
which,  when  examined  by  the  test,  yields  a  magnificent  display 
of  colors. 

2.  YWo~o  grain  leaves  a  quite  good  crystalline  residue,  which  yields, 

with  the  test,  results  very  similar  to  those  under  1.  The  same 
quantity  of  the  alkaloid  in  solution  in  one  grain  of  water  yields 
very  satisfactory  results. 

3.  Yo",¥To"  g^^ain :  the  residue  consists  of  a  number  of  well-defined 

crystals,  which,  when  treated  with  the  reagents,  yield  a  perfectly 
satisfactory  succession  of  colors.  The  results  obtained  from 
this  quantity  of  the  alkaloid,  when  free  from  foreign  matter 
and  manipulated  with  care,  are  just  as  satisfactory,  so  far  as  the 
evidence  of  the  presence  of  the  alkaloid  is  concerned,  as  those 
obtained  from  any  larger  quantity,  the  only  difference  being  in 
the  duration  of  the  different  colors. 


COLOR   TEST:    DELICACY.  565 

4.  THT.lhny  to'"'''"  •  ^''^'  r^'^'*!"*-'  usually  contains  a  number  of  distinct 

microscopic  crystals;  when  the  deposit  is  moistened  with  a  trace 
of  the  acid,  and  treated  with  a  mere  fraj^inent  of  the  potassium 
salt,  it  yields  very  satisfactory  evidence  of  the  presence  of  tiie 
alkaloid. 

5.  ^^__yi_^_jj.  grain :  if  the  residue  is  not  much  distributed,  it  usually 

contains  some  few  minute  crystals,  and,  when  treated  as  under  4, 
vields  a  very  distinct  coloration.  For  the  success  of  this  reac- 
tion it  is  essential  that  the  residue  be  deposited  within  a  narrow 
compass,  and  that  the  merest  trace  of  the  acid  and  color-develop- 
ing agent  be  employed.  Under  these  circumstances  it  will 
vield  quite  satisfactory  results.  The  acid  is  best  applied  by 
moistening  the  end  of  a  small  glass  rod  wnth  the  liquid  and 
then  drawing  it  over  the  deposit. 

When  collected  at  one  point,  and  perfectly  free  from  foreign 
matter,  even  a  much  smaller  quantity  of  strychnine  than  the  last- 
mentioned  will  yield,  under  the  action  of  the  test,  a  very  distinct 
purplish  or  violet  coloration,  especially  if  the  fragment  of  potassium 
dichromate  be  first  moistened  with  the  acid  and  then  brought  in 
contact  with  the  strychnine.  The  residues  obtained  from  solutions 
of  the  alkaloid  may  be  collected  within  a  small  space,  by  allowing 
the  liquid  to  evaporate  in  a  very  concave  watch-glass;  or,  better 
still,  as  first  advised  by  Messrs.  Rodgers  and  Girdwood,  by  collect- 
ing the  solution  in  a  pipette  provided  with  a  small  capillary  point, 
and  from  this  applying  a  minute  drop  of  the  liquid  to  a  warmed 
surface,  and  repeating  the  operation,  as  the  fluid  evaporates,  until  a 
sufficient  deposit  is  obtained. 

The  limit  of  this  test,  particularly  when  potassium  dichromate  is 
used  as  the  color-developing  agent,  has  been  the  subject  of  much 
misund^erstanding.  Thus,  with  this  reasrent  in  the  hands  of  some 
experimentalists,  the  test  failed  with  quantities  of  the  alkaloid  only  a 
little  less  than  the  l-2000th  or  l-3000th  of  a  grain.  But  that  these 
failures  were  not  due  to  any  want  of  delicacy  on  the  part  of  the 
method  itself  is  quite  apparent  from  the  foregoing  results.  So,  also, 
it  has  been  claimed  that  some  of  the  other  oxidizing  agents  are  more 
delicate  in  this  respect  than  potassium  dichromate;  and,  even,  that 
free  chromic  acid  is  much  more  delicate  than  its  potassium  salt. 
Since,  however,  this  salt,  when  properly  applied,  will  produce  a  dis- 
tinct coloration  with  the  least  quantity  of  strychnine  visible  to  the 


566  STEYCHNINE. 

naked  eye,  and  under  the  microscope  with  about  the  least  crystal 
visible  by  this  instrument,  it  is  obvious  that  it  reaches  the  possible 
practical  limit  of  any  of  the  color-developing  agents. 

It  is  not  thus  intended  to  imply  that  in  regard  to  delicacy  this 
method  is  superior  to  any  yet  proposed,  but  only  that  it  is  not  in- 
ferior :  similar  results  may  be  obtained  at  least  by  the  employment 
of  potassium  ferricyanide,  as  first  proposed  by  Dr.  E.  Davy,  and 
potassium  permanganate,  as  advised  by  Dr.  Guy,  and  also  manganese 
dioxide.  It  has  been  stated  by  some  observers  that  the  colors  pro- 
duced by  powdered  manganese  dioxide  and  lead  dioxide  are  much 
more  intense  than  those  produced  by  potassium  dichromate;  but  this 
is  true  only  of  given  quantities  of  the  alkaloid,  and  depends  upon 
the  physical  state  of  these  metallic  compounds,  similar  results  being 
equally  produced  by  finely-powdered  potassium  dichromate  or  potas- 
sium ferricyanide,  as  also  by  powdered  potassium  permanganate. 

Interferences. — Although  this  test  will  serve  to  reveal  the  nature 
of  the  least  visible  quantity  of  strychnine  when  in  its  j3Mre  state, 
yet  the  presence  of  certain  foreign  substances  may  cause  it  to  fail 
entirely,  even  when  comparatively  large  quantities  of  the  poison  are 
present.  In  this  respect  the  action  of  the  different  color-developing 
agents  is  about  equally  affected.  Brieger,  in  1850,  first  announced 
that  the  reaction  was  more  or  less  interfered  with  by  the  presence  of 
morphine  and  its  salts,  quinine,  and  sugar  ( Chem.  Gaz.,  viii.  408) ; 
and  since  then  it  has  been  asserted  that  brucine,  tartar  emetio,  nitrie 
add  and  nitrates,  common  salt,  corrosive  sublimate,  and  various  other 
substances,  had  a  similar  property.  Many  of  these  substances,  how- 
ever, even  when  present  in  relatively  large  quantity,  exercise  but 
little  influence  over  the  test ;  but  others  of  them  may  entirely  prevent 
its  ordinary  reaction. 

Morphine  belongs  to  the  latter  class  of  these  substances.  The 
influence  of  this  substance  is  determined  both  by  the  relative  and  the 
absolute  quantity  present.  Thus,  when  1-lOOth  of  a  grain  each  of 
strychnine  and  morphine,  or  of  their  salts,  are  thoroughly  mixed  by 
evaporating  their  mixed  solutions  to  dryness,  the  residue  yields,  under 
the  single  action  of  the  test,  little  or  no  indication  of  the  presence  of 
the  strychnine,  whereas  a  mixture  consisting  of  1— 1000th  of  a  grain 
each  of  the  alkaloids  yields  very  satisfactory  evidence  of  the  presence 
of  that  alkaloid.  In  other  words,  a  very  minute  quantity  of  a  mix- 
ture of  equal  j^arts  of  the  alkaloids  will  yield  much  better  results 


COLOR   TEST:    INTERFERENCES.  567 

tliuii  will  he  furnished  by  a  larger  quantity  of  the  mixture.  When 
the  niixtiiro  contains  tico  parts  of  morphine,  as  we  have  elsewhere 
shown  {('Item.  Ncics,  April,  18G0,  24.">),  the  strychnine  reaction  may 
still  be  obtained,  provided  only  a  small  quantity  of  the  mixture 
be  employed ;  but  in  the  presence  of  fhrc<'  parts  of  morphine  the 
reaction  is  no  longer  niarked,  even  with  a  minute  quantity  of  the 
mixture. 

When  these  alkaloids  exist  in  the  same  solution,  they  may  be 
separated  by  rendering  the  mixture  alkaline  and  agitating  it  with 
chloroform,  in  which  the  strychnine  is  very  freely  soluble,  whilst  the 
morphine  is  almost  wholly  insoluble,  especially  in  the  presence  of  a 
free  alkali.  It  is  therefore  obvious  that  when  strychnine  has  been 
extracted  from  organic  mixtures  by  means  of  chloroform  in  the 
manner  to  be  pointed  out  hereafter,  this  interference  on  the  part  of 
morphine  to  the  color  test  does  not  exist.  Experiments  show  that 
this  is  true,  under  certain  conditions,  of  the  chloroform  extract 
obtained  from  a  strongly  alkaline  mixture  containing  one  hundred 
parti  of  morphine  with  only  one  part  of  strychnine,  even  when  only 
1-lOOOth  grain  of  the  latter  alkaloid  is  present. 

It  is  obvious,  from  what  has  been  stated,  that  a  given  quantity  of 
chloroform  could  extract  from  an  alkaline  mixture  .of  strychnine  and 
morphine  only  a  very  minute  and  limited  trace  of  the  morphine, 
whether  only  that  trace  or  very  many  times  that  quantity  of  the 
alkaloid  was  })resent :  hence,  if  that  minute  quantity  (or  more)  of 
morphine  was  present  with  only  a  still  less  quantity  of  strychnine, 
the  chloroform  residue  might  then  fail  to  respond  to  the  color  test 
for  strychnine. 

Since  morphine  is  still  less  soluble  in  pure  ether  than  in  chloro- 
form, this  liquid  may  equally  be  employed  for  the  separation  of  these 
alkaloids,  especially  if  after  the  addition  of  the  alkali  the  mixture 
be  allowed  to  stand  some  minutes  before  being  agitated  with  the 
liquid.  It  should  be  remembered,  however,  that  strychnine  is  much 
less  soluble  in  ether  than  in  chloroform. 

For  the  separation  of  strychnine  and  morphine,  it  has  been 
proposed  to  precipitate  the  strychnine  by  a  solution  of  potassium 
dichromate.  But  as  this  reagent  also  jiroduces  precipitates  in  strong 
solutions  of  salts  of  morphine,  especially  after  standing  some  time, 
and,  also,  as  the  chromate  of  strychnine  is  but  little  less  soluble  in 
water  than  the  pure  alkaloid,  it  is  obvious  that  we  might  have  a 


568  STRYCHNINE. 

mixture  of  these  alkaloids  the  precipitate  from  which  would  consist 
largely,  or  even  entirely,  of  chromate  of  morphine ;  and,  moreover, 
that  even  under  the  most  favorable  circumstances  a  given  quantity 
of  the  strychnine  would  reinain  in  solution,  and  thus  entirely  escape 
detection.  In  the  presence  of  a  free  alkali  potassium  dichroraate  is 
converted,  in  part  at  least,  into  the  monochromate,  which  is  a  more  ' 
delicate  precipitant  of  morphine  than  of  strychnine. 

Brucine,  the  alkaloid  associated  with  strychnine  in  nux  vomica, 
has  the  property  even  perhaps  to  a  greater  extent  than  morphine 
of  disguising  the  color  reaction  of  strychnine.  Thus,  a  residue 
consisting  of  1-lOOth  grain  each  of  strychnine  and  brucine  fails  to 
give,  under  the  test,  any  indication  of  the  strychnine ;  a  mixture  of 
1— 1000th  grain  each  yields  only  a  faint  reaction ;  but  a  mixture  of 
l-10,000th  grain  each  of  the  alkaloids  yields  very  satisfactory  evi- 
dence of  the  presence  of  strychnine.  So,  also,  1-1 0,000th  grain  of 
strychnine  with  1-lOOOth  grain  of  brucine  yields  little  or  no  colora- 
tion ;  but  1-lOOth  grain  of  strychnine  with  1-1 000th  grain  of  brucine 
yields  a  very  marked  reaction,  although  somewhat  masked.  This 
interference  on  the  part  of  brucine  applies  equally  whether  potassium 
dichromate,  potassium  ferricyanide,  or  manganese  dioxide  be  era- 
ployed  as  the  oxidizing  agent. 

Although  commercial  strychnine  generally  contains  more  or  less 
brucine,  the  latter  is  perhaps  never  present  in  sufficient  proportion 
to  interfere  seriously  with  the  color  test  for  strychnine.  These  alka- 
loids may,  at  least  for  the  most  part,  be  separated,  if  not  in  only 
minute  quantity,  by  treating  a  strong  aqueous  solution  of  their 
sulphates  or  acetates  with  very  decided  excess  of  ammonia,  when 
the  strychnine  will  be  precipitated,  whilst  the  brucine  will  remain  in 
solution.  Or,  the  alkaloids  may  be  dissolved  in  hot  absolute  alcohol, 
which  on  cooling  will  deposit  the  strychnine,  the  brucine  remaining 
in  solution.  Messrs.  Dunstan  and  Short  have  recently  advised  a 
method,  based  upon  the  difference  in  the  solubility  of  the  ferro- 
cyanide  of  strychnine  and  brucine,  for  the  separation  of  the  two 
alkaloids.  {Amer.  Jour.  Pharm.,  Nov.  1883,  579.)  This  method, 
however,  applies  only  when  comparatively  large  quantities  of  the 
alkaloids  are  present. 

Nitrates,  such  as  potassium  nitrate,  interfere  with  the  normal 
reaction  of  the  test  to  nearly  or  about  the  same  extent  as  morphine; 
and  the  interference  applies  equally  to  the  different  color-developing 


COLOR  TEST:    1  AI.LACIKS.  569 

ai>;cMits.  Ill  ivt:;:ir(l  to  the  iiilluciice  oi"  tartar  emetic,  our  own  ohscrva- 
tioiis  fully  coiilinn  those  of  Mr.  Hagcn  {Chem.  Gaz.,  1857,  :i97), 
iiamelv,  that  this  substance  may  be  present  even  in  very  large  excess 
without  exerting  any  very  marked  inlluence;  yet,  when  the  mixture 
contains  twenty  or  thirty  parts  of  the  compound,  it  may  entirely 
disguise  the  ordinary  reaction  of  the  test.  These  observations  are 
equally  applicable  in  regard  to  the  modifying  influence  of  sugar. 
Since  the  nitrates,  tartar  emetic,  and  sugar  are  insoluble  in  chloro- 
form and  in  ether,  neither  of  these  substances  could  be  present  with 
strychnine  when  the  alkaloid  is  extracted  from  organic  mixtures  by 
either  of  these  liquids. 

A  much  more  serious  interference  to  this  test  than  any  yet  men- 
tioned is  the  presence  of  certain  undefined  organic  substances  fre- 
quently extracted  from  complex  mixtures  by  chloroform  and  by 
ether.  It  is  no  unusual  occurrence  thus  to  obtain  extracts  which 
fail  to  reveal  the  presence  of  strychnine,  even  when  comparatively 
large  quantities  of  the  alkaloid  are  purposely  added.  In  f\ict,  this 
is  so  frequently  the  case  when  only  a  very  minute  quantity  of  the 
poison  is  present,  that,  should  a  suspected  extract  fail  to  indicate  the 
presence  of  strychnine,  before  concluding  that  the  latter  is  entirely 
absent  it  may  be  best  to  add  to  a  separate  portion  of 'the  extract  a 
very  minute  quantity  of  the  pure  alkaloid  and  determine  whether 
the  failure  might  not  be  due  to  this  cause.  The  method  for  sepa- 
rating substances  of  this  kind  will  be  considered  hereafter. 

Fallacies. — It  has  been  objected  to  this  test  that  under  its  action 
various  other  substances,  as  aniline,  curarine,  cod-liver  oil,  pyrox- 
anthine,  papaverine,  narceine,  veratrine,  and  sokinine,  yield  colors 
somewhat  similar  to  or  even  identical  with  those  produced  from 
strychnine.  When,  however,  the  test  is  properly  applied  and  ob- 
served, these  objections  have  little  or  no  practical  force.  Thus,  all 
these  substances,  except  aniline,  unlike  strychnine,  yield  their  colors, 
or  at  least  are  colored,  by  sulphuric  acid  alone;  and,  furthermore, 
none  of  them,  except  curarine  and  cod-liver  oil,  even  by  the  con- 
joined action  of  the  acid  and  color-developing  agent,  yields,  like 
strychnine,  a  series  or  quick  succession  of  colors. 

Should,  however,  potassium  permanganate  be  employed  as  the 
oxidizing  agent,  a  more  or  less  blue  or  violet  coloration  may  be 
developed,  in  the  absence  of  strychnine,  by  various  other  organic  sub- 
stances besides  those  just  mentioned.    According  to  W.  T.  Sedgwick 


570  STRYCHNINE. 

{Amer.  Chem.  Jour.,  Dec.  1879,  369),  even  bits  of  filter-paper,  woody- 
fibre,  and  shreds  of  cloth  may  produce  under  this  reagent  colors 
closely  resembling  those  produced  by  strychnine.  From  an  infusion 
of  JEujjatoj'ium  perfoUatwn  (boneset)  this  observer  obtained,  under 
the  action  of  the  permanganate,  a  magnificent  bluish-purple  color, 
whilst  potassium  dichromate  and  manganese  dioxide  produced  no 
blue  coloration  whatever.  The  general  chemical  nature  of  some  of 
the  foregoing  fallacious  substances  may  now  be  briefly  considered. 

Aniline,  in  its  pure  state,  is  a  colorless  liquid,  having  a  rather 
pleasant  odor,  and  a  sharp,  acrid  taste :  it  is  obtained  from  coal-tar, 
and  by  the  action  of  potassium  hydrate  upon  indigo ;  it  may  also  be 
obtained  by  various  other  methods.  When  treated  with  concentrated 
sulphuric  acid,  it  undergoes  no  change  of  color,  but  throws  down,  if 
present  in  notable  quantity,  a  white  precipitate  of  aniline  sulphate. 
The  salts  of  this  base  are  colorless,  nearly  tasteless,  and,  for  the  most 
part,  readily  crystallizable.  The  sulphate  has  been  employed  as  a 
therapeutic  agent.  Pure  aniline  is  readily  soluble  in  chloroform, 
but  its  salts  are  almost  wholly  insoluble  in  this  liquid. 

When  the  salts  of  aniline  are  treated  with  concentrated  sulphuric 
acid,  they,  like  the  salts  of  strychnine,  yield  no  coloration ;  but 
when  a  crystal  of  potassium  dichromate,  or  a  small  portion  of  any 
of  the  other  oxidizing  agents,  is  stirred  in  the  acid  mixture,  the  latter 
slowly  acquires  a  yellowish  or  greenish  tint,  then  presents  bluish 
streaks,  and  after  a  little  time  assumes  a  beautiful  deep  blue  color, 
which  undergoes  little  or  no  change  for  half  an  hour  or  even  much 
longer,  but  finally  becomes  nearly  or  entirely  black.  It  is  thus 
obvious  that  the  reaction  of  this  substance  bears  but  little  similarity 
to  that  of  strychnine,  about  the  only  resemblance  being  in  the  pro- 
duction of  a  deep  blue  color.  But  in  the  case  of  strychnine,  as  re- 
marked by  Dr.  Guy,  this  color  is  the  first  produced,  and  is  developed 
either  immediately  or  at  most  within  a  few  moments,  and  is  quickly 
followed  by  other  characteristic  colors,  it  being  itself  exceedingly 
transient;  whereas  in  the  case  of  aniline  this  color  is  but  slowly 
developed,  is  preceded  by  other  colors,  and  when  once  established  is 
exceedingly  persistent,  and  ultimately  becomes  black.  Dr.  Letheby 
reports  {Chem.  News,  v.  71)  two  cases  of  accidental  poisoning  by 
nitro-benzole,  in  which  he  found  that  it  was  changed  in  the  animal 
body  into  aniline. 

Curarine  is  the  name  applied  to  the  active  principle,  or  alkaloid. 


COLOR   TKST:    FALLACIES.  571 

found  ill  Woorara,  or  Ciirara,  tlio  substiince  employed  by  the  Indians 
of  South  America  for  poisoning  their  arrows.  Much  doubt  exists 
as  to  the  true  nature  of  woorara.  Accordini;  to  Waterton,  it  is  pre- 
pared from  several  dilferent  ])lants,  two  species  of  poisonous  ants, 
and  the  rani2;s  of  certain  snakes;  while  S(^homl)urgk  states  that  it 
consists  of  vegetable  matter  alone,  and  chiefly  of  an  extract  of  the 
bark  of  the  Strychnos  toxifera,  a  tree  found  native  in  Guiana.  Vari- 
ous other  statements  have  been  made  in  regard  to  its  com{)osition. 
Tliat  there  are  at  least  several  varieties  of  this  substance  current 
among  the  dilferent  tribes  of  Indians  seems  to  be  fully  established 
by  the  investigations  of  Drs.  Hammond  and  Mitchell  {Amer.  Jour. 
Med.  Sci.,  July,  1859,  13-61);  and  it  is  even  probable  that  each 
tribe  hiis  its  own  method  for  preparing  the  poison.  It  was  formerly 
believed  that  the  poisonous  properties  of  woorara  \yQve  due  to  the 
presence  of  strychnine;  but  this  alkaloid  has  not  been  found  in  any 
of  the  specimens  yet  examined.  In  fact,  the  physiological  effects  of 
this  substance  are  the  very  opposite  to  those  of  strychnine,  and  it 
has  even  been  advised  as  an  antidote  in  poisoning  by  that  alkaloid. 

Woorara  is  usually  described  as  a  hard,  black  or  nearly  black, 
brittle,  resin-like  solid,  of  an  intensely  bitter  taste ;  in  the  state  of 
powder  it  has  a  dark  brown  color.  It  is,  for  the  ra9st  part,  readily 
soluble  in  water  and  in  alcohol,  but  is  only  very  slightly  acted  upon 
by  ethev  and  chloroform,  even  in  the  presence  of  a  free  alkali.  The 
statements  in  regard  to  the  chemical  properties  of  this  substance  have 
been  somewhat  conflicting.  The  active  principle,  or  curarine,  as  ob- 
tained by  MM.  Roulin  and  Boussingault,  who  were  the  first  to  isolate 
the  alkaloid,  was  in  the  form  of  a  transparent  solid,  having  a  pale 
yellow  color  and  an  exceedingly  bitter  taste.  It,  as  well  as  all  its 
salts,  was  uncrystallizable.  According  to  Bernard,  curarine  dissolves 
in  concentrated  sulphuric  acid  with  the  production  of  a  beautiful 
carmine  color;  and  Pelikan  states  that  under  the  combined  action  of 
this  acid  and  a  color-developing  agent,  as  potassium  dichromate  or  a 
current  of  electricity,  it  yields  a  brilliant  red  color.  It  would  appear 
that  M.  Preyer  obtained  curarine,  as  well  as  its  soluble  salts,  in  the 
crystalline  form.  [Chem.  News,  London,  July,  1865, 10.)  According 
to  this  observer,  the  pure  alkaloid  yields  with  concentrated  sulphuric 
acid  a  magnificent  and  lasting  blue  color ;  while  with  this  acid  and 
potassium  dichromate  it  yields  much  the  same  series  of  colors  as 
strychnine.     With  strong  nitric  acid  it  yields  a  purple  coloration. 


572  STRYCHNINE. 

A  specimen  of  ordinary  woorara,  kindly  furnished  us  in  liberal 
quantity  by  Dr.  S.  Weir  Mitchell,  has  the  following  properties,  its 
physical  appearances  being  the  same  as  those  just  described.  When 
treated  in  its  crude  state,  with  concentrated  sulphur ie  acid,  it  slowly 
yields,  without  entirely  dissolving,  a  reddish-brown  solution,  which, 
when  stirred  with  a  small  portion  of  potassium  dichromate,  or  any 
other  oxidizing  agent,  gives  a  series  of  colors  very  similar  to  that 
produced  from  a  very  impure  mixture  of  strychnine.  Concentrated 
nit7-iG  acid  dissolves  it,  witii  evolution  of  nitrous  fumes,  to  a  deep 
reddish-brown  solution.  It  is  for  the  most  part  readily  soluble  in 
water,  especially  upon  the  application  of  heat ;  the  insoluble  portion 
consists  apparently  of  vegetable  fragments.  The  filtered  aqueous 
solution  has  a  deep  brownish  color,  an  intensely  bitter  taste,  and  a 
just  perceptible  acid  reaction.  It  is  about  equally  soluble  in  strong 
alcohol.  The  concentrated  aqueous  solution  yields  with  a  solution 
of  potassium  dichromate  a  yellow,  amorphous  precipitate,  which, 
when  washed  and  treated  with  a  small  quantity  of  concentrated  sul- 
phuric acid,  yields  a  series  of  colors  not  to  be  distinguished  from 
that  produced  under  similar  circumstances  from  the  chromate  of 
strychnine.  This  precipitate,  however,  differs  from  the  strychnine 
compound  in  being  uncrystallizable,  and  rather  readily  soluble  in 
water. 

When  a  strong  aqueous  solution  of  several  grains  of  an  alcoholic 
extract  of  the  crude  poison  is  rendered  strongly  alkaline  with  potas- 
sium hydrate  and  agitated  with  chloroform,  this  liquid  remains  color- 
less, and  leaves,  upon  spontaneous  evaporation,  a  slight,  yellowish, 
gum-like  residue,  having  an  intensely  bitter  taste.  When  a  minute 
portion  of  this  residue  is  touched  with  a  drop  of  sulphuric  acid,  it 
acquires  a  red  color,  and  very  soon  dissolves  to  a  solution  of  the 
same  hue;  if  a  small  crystal  of  potassium  dichromate  be  now  stirred 
in  the  solution,  it  produces  a  series  of  colors  the  perfect  counterj)art 
of  that  from  strychnine,  with  perhaps  the  exception  that  the  blue  and 
purple  colors  are  somewhat  more  persistent  than  those  from  an  equal 
quantity  of  the  latter  substance.  Under  the  action  of  nitric  acid,  the 
chloroform  residue  assumes  a  red  color,  and  dissolves  to  a  reddish 
solution ;  this  color  is  discharged  by  heat,  and  the  cooled  liquid 
remains  unchanged  on  the  addition  of  stannous  chloride.  The 
alkaline  solution  from  which  the  chloroform  extract  was  obtained 
has  an  intensely  bitter  taste,  and  yields  with  a  solution  of  potassium 


COLOR    TKST:    FA  M,A('I  KS.  573 

iliclii'otiiiito  ;i  I'atlu'i'  coijious  aiii()i'|)li()iis  jd'ccipitati',  liuvinj^  tlie 
same  properties  as  tlie  precipitate  (Vdim  an  aqueous  solution  of 
the  crude  poison.  When  a  small  quantity  of  tlie  alkaline  solution 
is  treated  with  sulphuric  acid,  it  acquires  a  i)eautii"ul  purple  color, 
which  on  the  addition  of  a  crystal  of  potassium  dichromate  is  changed 
to  a  deep  !)Iue,  followed  by  purple  and  the  other  characteristic  colors. 
The  alkaline  solution  also  yields  other  reactions,  indicatint;  that  but 
little  of  the  active  j)rinciple  had  been  removed  by  the  chloroform. 
Various  efforts  were  made  to  obtain  this  princi})le,  and  some  of  its 
compounds,  in  the  crystalline  state,  but  in  all  cases  without  success. 

Tt  thus  apjiears  that  this  sample  of  woorara  contains  a  principle 
having  certain  chemical  properties  in  common  with  strychnine. 
Thus,  like  strychnine,  it  has  an  intensely  bitter  taste;  yields  under 
the  combined  action  of  sulphuric  acid  and  an  oxidizing  agent  a 
])articular  series  of  colors;  and  its  potassium  dichromate  precipitate 
yields,  with  this  acid  alone,  similar  results.  But  these  are  about  the 
only  respects  in  which  it  resembles  that  alkaloid.  Among  the  dif- 
ferences existing  between  this  ])rinciple,  at  least  in  the  sample  under 
consideration,  and  strychnine,  may  be  mentioned  the  following:  it 
and  all  its  compounds  are  uncrystallizahJe ;  it  is  colored  by  sulphuric 
acid  alone;  its  potassinm  dichromate  precipitate  is  rather  readily 
soluble  in  water,  and  is  araorj)hous;  it  is  almost  wlwlly  mso/u6?e  in 
chloroform,  and  readily  soluble  in  potassium  hydrate;  and  its  solu- 
tions are  not  precipitated  by  the  caustic  alkalies. 

Three  grains  of  the  above  woorara  administered  in  solution  to 
a  young  cat  produced  no  appreciable  eflFect  whatever ;  although  the 
animal  w^as  closely  watched  for  twelve  hours.  But  a  very  small 
quantity  of  the  paste  introduced  under  the  skin  of  the  inside  of  the 
thigh  of  a  similar  animal  produced  almost  immediate  stupor,  and 
in  eight  minutes  complete  prostration;  this  condition  continued, 
with  occasional  convulsive  movements,  for  some  hours,  after  which 
the  animal  completely  recovered. 

Cod-liver  oil  has  also  been  mentioned  as  a  source  of  fallacy.  This 
substance  when  treated  with  sulphuric  acid  alone  yields  a  series  of 
colors  which  might  be  confounded  with  that  produced  from  strych- 
nine by  the  combined  action  of  this  acid  and  an  oxidizing,  agent. 
But  as  strychnine  yields  no  coloration  with  sulphuric  acid  alone,  it 
is  obvious  that  when  the  acid  is  applied  first  and  its  action  observed, 
all  grounds  for  objection,  so  far  as  this  oil  is  concerned,  are  at  once 


574  STRYCHNINE. 

removed.  Moreover,  the  physical  state  of  cod-liver  oil  would  at 
once  distinguish  it  from  strychnine,  or  any  of  its  salts,  in  the  solid 
state. 

The  objections  in  regard  to  the  other  substances  heretofore  men- 
tioned have  already  been  answered,  namely,  that  they  are  colored  by 
sulphuric  acid  alone,  and  under  no  circumstance  do  they  yield  a 
quick  succession  of  colors.  Thus,  pyroxanthine,  which  has  a  bright 
red  color,  yields  with  the  acid  a  blue  solution ;  papaverine,  a  purple ; 
narceine,  a  reddish-yellow  or  brownish ;  veratrine,  a  yellow,  slowly 
becoming  crimson ;  and  solanine,  an  orange-brown  mixture.  It  may 
be  remarked  that  the  exact  tint  of  color  produced  by  the  acid  with 
at  least  some  of  these  substances  is  more  or  less  modified  by  the 
quantity  of  material  employed. 

In  addition  to  the  substances  now  considered,  there  are  a  number 
of  alkaloids  and  other  organic  proximate  principles  which,  when 
treated  either  with  sulphuric  acid  alone  or  with  this  acid  and  potas- 
sium dichromate,  give  rise  to  more  or  less  coloration.  The  action  of 
this  test  with  a  number  of  these  substances  was  first  examined  by 
M.  Eboli  {Chem.  Gazette,  1856,  251);  then  by  Dr.  T.  E.  Jenkins,  of 
Louisville,  Ky.,  who  extended  the  investigation  to  about  fifty  of  these 
principles  {Semi- Monthly  Med.  News,  April,  1859,  214) ;  and  still  more 
recently  by  Dr.  Guy,  of  London  (Chemical  News,  Aug.  1861,  113), 
who  added  some  sixteen  substances  to  those  examined  by  Dr.  Jenkins. 
But  of  all  the  substances  thus  and  since  examined,  exclusive  of  some 
already  mentioned,  none  gave  results  resembling  the  reactions  of 
strychnine,  even  to  the  extent  of  those  already  considered. 

Galvanic  Test. — This  in  principle  is  the  same  as  the  preceding 
method,  only  that  the  oxygen  is  rendered  nascent  by  a  current  of 
voltaic  electricity,  instead  of  being  evolved  from  a  metallic  oxide,  by 
means  of  sulphuric  acid.  It  may  be  applied,  according  to  Dr. 
Letheby,  who,  we  believe,  first  advised  the  process  (Lancet,  June, 
1856,  708),  by  placing  a  drop  of  the  strychnine  solution  in  a  cup- 
shaped  depression  made  in  a  piece  of  platinum-foil,  evaporating  the 
liquid  at  a  low  temperature,  and  moistening  the  residue  with  a  small 
drop  of  concentrated  sulphuric  acid.  The  foil  is  then  connected  with 
the  platinum  pole  of  a  single  cell  of  Grove's  or  Smee's  battery,  and 
the  acid  liquid  touched  with  the  platinum  terminal  of  the  negative 
pole.  In  a  moment  the  violet  coloration  manifests  itself  in  great 
intensity. 


POTASSIUM    IODIDE   TEST.  575 

III  reo;ar(l  to  the  doHcaoy  of  this  method,  it  is  much  the  same  as 
that  of  tlie  test  as  ordinarily  applied.  Thus,  according  to  our  own 
ex|)eriments,  the  1-1 0,000th  of  a  grain  of  strychnine  yields  a  fine 
display  of  colors;  and  the  l-100,000th  of  a  grain,  a  distinct  re- 
action. Since,  however,  this  process  is  not  so  readily  applied,  and 
is  about  equally  open  to  the  interferences  and  so-called  fallacies  that 
hold  against  the  ordinary  method,  it  seems  to  possess  no  advantage 
over  the  latter.  In  fact,  for  the  detection  of  very  minute  traces  of 
strychnine  it  is  less  satisfactory  than  the  ordinary  method. 

3.  Potasmim  Sulphocyanide. 

This  reagent  throws  down  from  solutions  of  salts  of  strychnine, 
when  not  too  dilute,  a  white  crystalline  precipitate  of  strychnine  sul- 
phocyanide, which,  according  to  Nicholson  and  Abel,  has  the  com- 
position CojH^vjNoOjjHCyS.  The  precipitate  is  insoluble  in  excess 
of  the  precipitant,  and  but  sparingly  soluble  in  diluted  acetic  and 
hydrochloric  acids. 

1.  Yw  gi'sin  of  strychnine,  in  one  grain  of  water,  yields  an  imme- 

diate crystalline  deposit,  and  in  a  few  moments  the  mixture 
becomes  a  nearly  solid  mass  of  crystals,  of  the  forms  shown  in 
Plate  X.,  fig.  2. 

2.  YoVu  grain  :  on  stirring  the  mixture,  in  a  very  little  time  it  throws 

down  crystals,  and  soon  there  is  a  very  satisfactory  deposit. 

3.  57nro  grain  yields,  especially  if  the  mixture  be  stirred,  after  some 

minutes,  a  satisfactory  deposit  of  crystalline  needles. 
Potassium  sulphocyanide  also  produces  white  crystalline  precipi- 
tates in  solutions  of  several  other  alkaloids. 

4.  Potassium  Iodide. 

Somewhat  strong  solutions  of  salts  of  strychnine  yield  with  potas- 
sium iodide  a  white  crystalline  precipitate,  which  is  insoluble  in 
excess  of  the  precipitant  and  in  the  free  alkalies,  and  only  slowly 
soluble  in  large  excess  of  acetic,  nitric,  and  hydrochloric  acids. 
The  formation  of  the  precipitate  is  much  facilitated  by  stirring  the 
mixture  with  a  glass  rod. 

1.  Yoo"  gi'^in  of  strychnine:  in  a  few  moments  the  mixture  becomes 
a  nearly  solid  mass  of  crystals,  of  the  same  forms  as  those  pro- 
duced by  the  preceding  reagent  (Plate  X.,  fig.  2). 


576  STEYCHJS^INE. 

2.  YWWQ   gi'^^"  •  after  a  few   minutes,  especially  if  the  mixture  be 

stirred,  a  quite  good  deposit  of  stellate  groups  of  crystals. 

3.  g-oVo"  gi'aiu  :  after  several   minutes  there  is  a  quite  satisfactory 

crystalline  deposit. 
The  precipitates    produced  by  this  and   the   preceding   reagent 
cannot  readily  be  confirmed  by  the  color  test. 

5.  Potassium  Dichr ornate. 

This  reagent  produces  in  solutions  of  salts  of  strychnine  a  bright 
yellow  precipitate  of  strychnine  chromate,  which  almost  immediately 
becomes  crystalline.  The  precipitate  is  insoluble  in  excess  of  the 
precipitant,  and  in  acetic  acid,  and  only  very  sparingly  soluble  in 
diluted  nitric  acid,  but  readily  soluble  in  the  concentrated  acid.  The 
fixed  caustic  alkalies  slowly  decompose  the  precipitate,  with  the 
elimination  of  pure  strychnine,  which,  unless  from  dilute  solutions, 
assumes  the  crystalline  form,  and  may  be  extracted  by  chloroform. 
This  liquid  will  also  extract  portions  of  the  pure  alkaloid  from 
aqueous  mixtures  of  the  chromate,  without  dissolving  a  trace  of  the 
latter.  From  dilute  solutions  of  strychnine  the  reagent  produces  no 
immediate  precipitate,  but  the  latter  separates  after  a  time  in  the 
crystalline  form;  under  these  circumstances  the  formation  of  the 
precipitate  is  much  facilitated  by  stirring  the  mixture  with  a  glass 
rod. 

1,  ^A_  grain  of  strychnine  yields  a  very  copious  precipitate,  which 

in  a  very  little  time  becomes  a  dense  mass  of  bush-like  crystals. 

2,  g^  grain  :  an  immediate  deposit,  and  very  soon  a  copious,  crys- 

talline precipitate.  If  after  the  addition  of  the  reagent  the 
mixture  be  allowed  to  remain  quiet,  the  precipitate,  after  a 
little  time,  forms  beautiful  dendroidal  groups  of  crystals,  Plate 
X.,  fig.  3. 

3,  ^^1^^  grain  yields  no  immediate  precipitate,  but  very  soon  crystals 

appear,  and  in  a  few  minutes  there  is  a  quite  good  deposit.  If 
the  mixture  be  stirred,  it  quickly  yields  a  very  good  crystalline 
precipitate. 

4,  yJL^  grain :  on  stirring  the  mixture  for  a  few  moments  it  yields 

streaks  of  granules  along  the  path  of  the  glass  rod,  and  soon 
a  quite  good  deposit  of  octahedral  and  bush-like  crystals,  Plate 
X.,  fig.  4. 

5,  ^-JL_^  grain :  if  the. mixture  be  stirred,  after  some  minutes  a  very 


POTASSIUftr    DICHROMATE   TEST.  577 

satisfactory  deposit  of  small  octahedral  crystals  and  plates  ap- 
pear. 
^'  Tff.ro'o  y;'"dii :  when  treated  with  a  small  quantity  of  reagent 
and  the  mixture  stirred,  it  yields,  after  several  minutes,  small 
granules;  after  about  twenty  minutes  there  is  a  very  satisfac- 
tory microscopic  crystalline  deposit  of  long  plates,  granules, 
and  small  octahedral  crystals. 

If  the  supernatant  liquid  be  decanted  from  any  of  the  above 
deposits,  and  the  dried  crystals  touched  with  a  small  drop  of  concen- 
trated sulphuric  acid,  they  immediately  assume  a  magnificent  blue 
color,  quiclvly  changing  to  purple  or  violet,  and  dissolve  to  a  purple 
or  violet  solution,  which,  passing  through  various  shades,  becomes 
red,  then  slowly  fades  iu  color.  In  other  words,  these  crystals  may 
be  confirmed  by  the  color  test  by  the  simple  addition  of  suljihuric 
acid.  The  precipitate  obtained  from  the  l-10,000th  of  a  grain  of 
strychnine,  iu  solution  in  one  grain  of  water,  will,  in  this  manner, 
yield  a  magnificent  display  of  colors;  and  even  the  least  microscopic 
crystal  of  the  compound,  when  touched  under  this  instrument  with  a 
very  minute  drop  of  the  acid,  will  yield  a  very  distinct  coloration. 
It  must,  however,  be  borne  in  mind  that  a  solution  of  strychnine 
may  be  too  dilute  to  yield  any  precipitate  whatever  with  this  reagent, 
and  yet  have  a  distinctly  bitter  taste,  and  leave  up6n  spontaneous 
evaporation,  even  of  a  single  drop  of  the  solution,  a  residue,  which 
when  examined  by  the  color  test  in  the  ordinary  manner,  will  yield 
very  satisfactory  results.  Statements  have  been  made  in  regard  to 
the  delicacy  of  this  test  which  are  well  calculated  to  lead  to  erro- 
neous conclusions. 

For  the  separation  of  the  precipitate,  for  the  application  of  this 
confirmatory  reaction,  from  dilute  solutions  of  the  alkaloid,  it  is  best 
to  stir  the  mixture,  by  means  of  a  glass  rod,  in  a  watch-glass,  and 
then  allow  it  to  repose  for  about  half  an  hour,  when  the  crystallized 
deposit  M'ill  be  found  strongly  adherent  to  the  glass,  and  thus  permit 
the  ready  separation  of  the  supernatant  liquid  by  decantation.  Or, 
the  mixture  may  be  allowed  to  evaporate  spontaneously  to  dryness, 
and  the  residue  touched  with  a  drop  of  pure  water,  which  will  readily 
dissolve  any  excess  of  the  reagent  present,  while  the  attached  crystals 
of  the  strychnine  compound  will  remain. 

As  potassium  dichromate  also  produces  yellow  crystalline  precipi- 
tates with  brucine,  narceine,  codeine,  and  some  few  other  principles, 

37 


578  STRYCHNINE. 

and  amorphous  deposits  with  morphine,  narcotine,  and  a  number  of 
other  substances,  it  is  obvious  that  the  mere  production  of  even  a 
crystalline  precipitate  by  this  reagent  is  not  in  itself  positive  evidence 
of  the  presence  of  strychnine.  However,  the  crystalline  form  of 
the  strychnine  compound  as  usually  produced  is  somewhat  peculiar; 
and  when  the  crystals  yield  a  positive  reaction  with  sulphuric  acid, 
the  results  are  perfectly  unequivocal.  Even  a  positive  reaction  by 
this  acid  from  an  amorphous  deposit  would  exclude  every  other 
known  substance,  except  the  active  principle  of  certain  kinds  of  the 
woorara  poison.  By  this  method,  therefore,  the  two  most  charac- 
teristic tests  yet  known  for  the  recognition  of  strychnine  may  be 
applied  to  the  same  quantity  of  the  poison. 

Chroinate  of  Strychnine  which  had  been  preserved  for  some  years, 
when  touched  with  sulphuric  acid  failed  to  yield  satisfactory  colora- 
tions; but  on  the  addition  of  a  mineral  alkali  and  extraction  with 
chloroform,  the  alkaloid  was  recovered  unchanged. 

Potassium  Monochromate  occasions  no  precipitate  in  neutral 
solutions  of  salts  of  strychnine,  unless  they  be  very  concentrated. 
But  with  acidulated  solutions — provided  they  do  not  contain  very 
large  excess  of  a  mineral  acid — it  produces  results  similar  to  those 
by  the  dichromate,  due  to  the  fact  that  the  free  acid  converts  the 
reagent,  in  part  at  least,  into  the  latter  salt.  One  grain  of  a  1-lOOth 
neutral  sohition  of  the  alkaloid  yields,  especially  after  a  little  time, 
a  quite  good  crystalline  deposit,  very  similar  to  that  produced  by 
potassium  sulphocyanide  (Plate  X.,  fig.  2).  This,  however,  is  very 
nearly  the  limit  of  the  reaction  of  the  reagent  under  these  conditions. 

6.  Auric  Chloride. 

Trichloride  of  gold  produces  in  solutions  of  salts  of  strychnine, 
even  when  highly  dilute,  a  yellowish,  amorphous  precipitate,  which 
after  a  time  becomes  more  or  less  crystalline.  The  precipitate  is 
insoluble  in  acetic  acid,  and  only  sparingly  soluble  in  diluted  nitric 
acid ;  when  treated  with  potassium  hydrate,  it  slowly  assumes  a  dark 
color. 

1.  Y^  grain  of  strychnine,  in  one  grain  of  water,  yields  a  very 
copious  deposit,  which  at  first  has  an  orange-yellow  color,  but 
soon  becomes  yellow  and  more  or  less  crystalline,  forming 
groups  of  bush-like  crystals  and  granules.  If  the  precipitate 
contains  even  but  little  foreign  matter,  it  may  remain  amorphous. 


PLATINIC   CHLORIDE   TEST.  579 

2.  xif(rtr  ?^''f^''> '  '^  copious,  yellow  precipitate,  which  in  a  little  time 

becomes  converted  into  jrroups  of  crystals,  Plate  X.,  fij^.  5. 

3.  "nj-.Voir  gi''*'"  '  a  very  satisfactory,  yellowish  deposit,  which  soon 

yields  small  crystalline  groups. 

4.  -j-s-.ViTiJ  g''ii'"  •  '<^  very  satisfactory  turi)i(lity. 

5.  3-(7.^0-^(5-  grain  yields  a  very  distinct  cloudiness. 

When  the  precipitate  from  ten  grains  of  a  l-5000th  or  more 
dilute  solution  of  the  alkaloid  is  boiled  in  the  mixture,  the  deposit 
dissolves  to  a  clear  yellow  solution,  and  it  is  redeposited  with  little 
or  no  change  as  the  liquid  cools;  the  precipitates  from  stronger  solu- 
tions, when  treated  in  this  manner,  do  not  entirely  dissolve,  but 
undergo  more  or  less  decomposition,  with  the  deposition  of  metallic 
gold  uj)on  the  sides  of  the  tube.  Potassium  hydrate  dissolves  the 
precipitate  from  a  l-5000th  solution  to  a  clear  liquid ;  but  the  deposit 
from  stronger  solutions  is  not  readily  soluble  in  this  mineral  alkali. 
Upon  the  application  of  heat,  the  potassium  solution  acquires  a 
purplish  color  and  throws  down  a  precipitate. 

Auric  chloride  also  produces  yellow  precipitates  with  many  other 
substances,  but  the  crystalline  form  of  the  strychnine  deposit  is  some- 
what peculiar.  The  formation  of  these  crystals,  however,  as  already 
intimated,  is  readily  interfered  with  by  the  presence  of  foreign  matter. 

The  true  nature  of  the  strychnine  precipitate,  when  in  not  too 
minute  quantity,  may  be  established  by  gently  evaporating  the  mix- 
ture to  dryness,  treating  the  residue  with  a  small  drop  of  sulphuric 
acid,  and  then  stirring  in  the  mixture  a  minute  crystal  of  potassium 
dichromate,  when  the  strychnine  series  of  colors  will  be  developed. 
The  residue  from  1-lOOth  grain  of  strychnine  will  in  this  manner 
readily  yield  satisfactory  results;  but  1-lOOOth  grain  yields  little  or 
no  coloration.  This  reaction  is  much  interfered  with  by  the  presence 
of  large  excess  of  the  gold  reagent. 

7.  Platinio  ChloHde. 

This  reagent  produces  in  solutions  of  salts  of  strychnine  a 
pale  yellow,  amorphous  precipitate  of  strychnine  chloroplatinate, 
2C2iH22X202)HCl ;  PtCI^,  which  soon  becomes  crystalline.  The 
precii)itate,  especially  when  it  has  assumed  the  crystalline  form,  is 
insoluble  in  acetic  and  diluted  nitric  acids:  it  is  unchanged  in  color 
and  only  sparingly  soluble  in  the  caustic  alkalies. 


580  STRYCHNINE. 

1.  YDTT  grain  of  strychnine  yields  a  very  copious  precipitate,  which 

soon  becomes  a  mass  of  crystals. 

2.  YWTo  gi'aij'i  •  a  very  good  deposit,  which  is  soon  converted  into 

beautiful  crystals,  Plate  X.,.  fig.  6. 

3.  QQ-QQ  grain  :  on  stirring  the  mixture  it  yields  after  a  few  moments 

a  granular  deposit,  and  after  a  few  minutes  a  quite  good  crystal- 
line precipitate. 

4.  3-g-,VoT  gJ^aiii  yields  after  a  little  time,  if  the  mixture  has  been 

stirred,  a  quite  satisfactory  deposit  of  stellate  groups  of  crystals 
and  granules. 
This  reagent  also  produces  yellow  crystalline  precipitates  with 
nicotine,  potassium  compounds,  and  ammonia;  a  granular  deposit 
with  morphine;  and  amorphous  precipitates  with  a  number  of  sub- 
stances ;  but  the  strychnine  precipitate  is  usually  readily  distinguished 
from  these  by  its  crystalline  form.  In  mixtures  containing  much 
foreign  organic  matter,  however,  the  strychnine  compound  may  not 
assume  the  crystalline  state. 

Palladium  Chlotide  throws  down  from  solutions  of  salts  of  strych- 
nine a  yellow  precipitate,  which  assumes  the  same  crystalline  form  as 
that  produced  by  the  platinum  reagent ;  the  limit  of  the  reaction  is 
also  the  same. 

8.  PicriG  Acid. 

An  alcoholic  solution  of  this  acid  occasions  in  solutions  of  salts 
of  strychnine  a  yellow  precipitate  of  strychnine  picrate,  which  is  only 
sparingly  soluble  in  large  excess  of  acetic  acid  and  in  alcohol.  The 
precipitate  is  readily  soluble,  to  a  colorless  solution,  in  sulphuric  acid, 
and  the  mixture,  when  treated  with  a  color-developing  agent,  yields 
the  peculiar  strychnine-series  of  colors ;  not,  however,  in  the  same 
intensity  as  many  of  the  other  salts  of  the  alkaloid. 

1.  Y^  grain  of  strychnine  yields  a  very  copious,  amorphous  precipi- 

tate, which  slowly  becomes  converted  into  a  mass  of  irregular 
crystalline  tufts. 

2.  Yrro  gi'^in  •  ^  very  good  precipitate,  which  soon  becomes  changed 

into  crystals,  having  the  very  singular  forms  illustrated  in  Plate 
XL,  fig.  1. 

3.  i-Q.Voo"  grain  •  on  stirring  the  mixture  it  yields,  after  a  little  time, 

a  very  satisfactory  granular  deposit. 

4.  -2-6,VoT  grain  yields  after  a  little  time,  if  the  mixture  has  been 

stirred,  a  quite  perceptible  granular  precipitate. 


POTASSIUM    lODOIIVmt AROYRATE    TEST.  581 

Picric  acid  also  protluces  crystal  line  precipitates  with  various 
other  substances.  The  crystalline  form,  however,  of  the  strychnine 
coni|)ound  is  somewhat  peculiar. 

9.   CoiTosive  Sublimate. 

Mercuric  chloride  throws  down  from  stroni!;  neutral  solutions  of 
salts  of  strychnine  a  white,  amorphous  precipitate  of  the  double 
cldoridc  of  strychnine  and  mercury  which  is  readily  soluble  in  acids, 
even  acetic  acid.     After  a  time  the  precipitate  becomes  crystalline. 

1.  yJt  gJ'^i"  <^f  strychnine  yields  a  very  copious  precipitate,  which 

in  a  little  time  becomes  somewhat  granular,  then  changes  into 
groups  of  radiating  crystals,  usually  attached  to  a  granular 
nucleus,  and  aggregations  of  large  granules,  Plate  XI.,  fig.  2. 
The  general  form  of  these  crystals  is  readily  modified  by  slight 
circumstances. 

2.  3-J-^  grain:  after  some  minutes  the  mixture  yields  a  quite  satis- 

factory precipitate  of  stellate  crystals. 
In  solutions  but  little  more  dilute  than  the  last-mentioned,  the 
reagent  fails  to  produce  a  precipitate,  even  after  long  repose. 

10.  Potassium  lodohydrargyrate. 

This  reagent  may  be  prepared  by  dissolving  one  part  of  pure 
corrosive  sublimate  in  one  hundred  parts  of  water  and  then  adding 
just  sufficient  potassium  iodide  to  redissolve  the  scarlet  precipitate 
first  produced,  which  will  require  very  nearly  four  parts  of  the  iodine 
compound.  A  small  quantity  of  this  mixture  throws  down  from 
solutions  of  salts  of  strychnine  a  dull  white  precipitate  of  the  double 
iodide  of  strychnine  and  mercury,  which  is  insoluble  in  excess  of 
the  precipitant  and  in  the  caustic  alkalies,  as  well  as  in  acetic  and 
hydrochloric  acids.  The  precipitate  is  also  insoluble  in  alcohol ;  con- 
centrated sulphuric  acid  readily  decomposes  it,  with  the  production 
of  a  reddish-brown  or  purplish  color. 

1.  Yoir  gr^^^  of  strychnine,  in   one  grain  of  water,  yields  a  very 

copious  curdy  precipitate,  which  after  a  little  time  becomes  partly 
converted  into  granules  and  short,  crystalline  needles.  If  the 
reagent  contain  an  excess  of  potassium  iodide,  the  precipitate 
assumes  the  same  crystalline  form  as  when  this  salt  alone  is 
employed  as  the  precipitant. 

2.  Y^^  grain  yields  a  rather  copious  precipitate. 


582  STRYCHNINE. 

3.  ^Q^^QQ    grain :  a  quite  good  precipitate,  which   in  a  little  time 

becomes  converted  into  opaque  granules  and  short,  irregular 
needles.  On  the  addition  of  a  few  drops  of  acetic  or  hydro- 
chloric acid,  the  precipitate  is  soon  changed  into  irregular  groups 
of  rather  long  needles. 

4.  -so-.Too"  grain  yields  a  quite   distinct  precipitate,  and  in  a  little 

time  a  very  satisfactory  deposit.  This  deposit  is  very  similar 
in  appearance  to  that  produced  from  dilate  solutions  of  atropine 
by  bromohydric  acid,  as  illustrated  in  Plate  XII.,  fig.  6. 

6,  YoT/oTo"  gi"^iD  '•  ^^  immediate  change,  but  in  a  very  little  time 
the  mixture  becomes  cloudy,  and  soon  yields  a  very  satisfactory 
deposit  of  opaque  granules  and  short,  irregular  needles. 
The  production  of  a  white  precipitate  by  this  reagent  is  common 

to  solutions  of  most,  if  not  all,  of  the  alkaloids. 

11.  Potassium  Ferrieyanide. 

This  reagent  produces  in  quite  strong  neutral  solutions  of  salts 
of  strychnine  a  yellowish,  amorphous  precipitate,  which  in  a  little 
time  becomes  crystalline.  The  precipitate  is  only  slowly  soluble  in 
acetic  acid,  but  readily  soluble  in  the  stronger  acids,  and  is,  therefore, 
not  produced  in  their  presence. 
1.  YFo   gJ^ai^  of  strychnine  yields  a  quite  copious  precipitate,  which 

in  a  few  moments  becomes  converted  into  a  mass  of  beautiful 

groups  of  crystals,  Plate  XL,  fig.  3. 
2.'  -g^  grain  :  a  very  good  crystalline  precipitate. 
3.  yqTq  g^s-i''^  yields  little  or  no  indication  of  the  presence  of  the 

strychnine,  even  after  the  mixture  has  stood  half  an  hour  or 

longer. 
When  a  small  portion  of  the  precipitate,  occasioned  by  this  re- 
agent, is  treated  with  a  drop  of  concentrated  sulphuric  acid,  it,  like 
that  produced  by  potassium  dichromate,  dissolves  with  the  produc- 
tion of  the  same  series  of  colors  as  obtained  by  the  color  test  as 
ordinarily  applied.  The  least  visible  crystal  of  the  deposit  will  re- 
spond to  this  reaction.  It  will  be  observed,  however,  that  as  a 
precipitant  for  strychnine,  potassium  ferrieyanide  in  point  of  deli- 
cacy is  far  inferior  to  potassium  dichromate. 

Sodium  Nitroprusside  throws  down  from  neutral  solutions  of  salts 
of  strychnine  a  white  or  dirty-white  precipitate,  which  assumes  the 
same  crystalline  form  as  that  produced  by  potassium  ferrieyanide, 


IODINE   TEST.  583 

and  the  limit  of  the  reaction  is  about  the  same.  Bnt,  notwithstand- 
ing^ the  contrary  has  been  asserted,  this  precipitate,  unlike  that  occa- 
sioned by  potassium  ferricyanide,  dissolves  without  change  of  color 
in  concentrated  sulphuric  acid. 

Pofasmim  Fcrroci/anide  fails  to  precijiitate  solutions  of  salts  of 
strychnine,  unless  very  concentrated  and  perfectly  neutral.  One 
grain  of  a  1-lOOtli  solution  of  the  alkaloid  will  yield  a  quite  good 
crystalline  deposit;  but  this  is  very  nearly  the  limit  of  the  reaction. 

12.  Iodine  in  Potassium  Iodide. 

An  aqueous  solution  of  iodine  in  potassium  iodide  produces  in 
solutions  of  salts  of  strychnine,  even  when  highly  diluted,  a  reddish- 
brown,  amorphous  precipitate,  which  is  readily  soluble  in  alcohol, 
but  only  very  sparingly  soluble  in  acetic  acid.  The  precipitate  is 
readily  soluble  in  potassium  hydrate,  but  it  is  soon  replaced  by  a 
white  deposit.  Dr.  W.  B.  Herapath  has  shown  [Chem.  Gaz.,  1855, 
320)  that  an  alcoholic  solution  of  strychnine  yields  with  iodine, 
crystalline  compounds  having  very  peculiar  optical  properties. 

1.  Yoo"  grain  of  strychnine  yields  a  very  copious  deposit,  which  after 

a  time  becomes  more  or  less  crystalline. 

2.  YWW5  grain  :  a  copious  precipitate,  which  after  a  time  becomes,  in 

part  at  least,  converted  into  crystals,  Plate  XI.,  fig.  4.  These 
crystals  are  most  readily  obtained  when  large  excess  of  the 
reagent  is  avoided. 

3.  YO","oTo  gi'ain  yields  a  very  good  precipitate,  which  readily  dis- 

solves to  a  colorless  solution  in  potassium  hydrate,  but  after  a 
little  time  the  mixture  becomes  turbid.  The  precipitate  is 
slowly  converted  into  crystalline  nodules. 

4.  3i5-,-g-(nr  grain  yields  a  very  satisfactory  deposit. 

5.  TTTtT/Diru"  gi'3'Jn  furnishes  a  very  distinct  turbidity. 

This  reagent  also  produces  precipitates  with  various  organic  sub- 
stances, and  with  certain  inorganic  compounds,  but  the  character  of 
the  strychnine  crystals  is  quite  peculiar;  their  formation,  however,  is 
readily  interfered  with  by  the  presence  of  foreign  matter. 

The  strychnine  may  be  recovered  from  the  washed  precipitate  by 
dissolving  the  latter  in  strong  alcohol,  and  treating  the  solution  with 
slight  excess  of  silver  nitrate,  which  will  precipitate  the  iodine  as 
silver  iodide;  this  is  removed  by  a  filter,  and  the  excess  of  the 
silver  reagent  precipitated  from  the  filtrate  by  the  cautious  addition 


584  STRYCHNINE. 

of  diluted  hydrochloric  acid ;  the  silver  chloride  thus  produced  is 
then  separated  by  a  filter,  and  the  filtrate  evaporated  to  dryness  on  a 
water-bath,  when  the  strychnine  will  be  left  in  its  pure  state.  This 
method  will  serve  for  the  recovery  of  even  extremely  minute  quan- 
tities of  the  alkaloid. 

13.  Bromine  in  Bromohydrie  Acid. 

A  strong  aqueous  solution  of  bromohydrie  acid  saturated  with 
bromine  occasions  in  solutions  of  salts  of  strychnine,  even  when 
very  dilute,  a  yellow,  amorphous  precipitate,  which  is  readily  soluble 
in  alcohol,  and  in  acetic  acid.     The  precipitate  remains  amorphous. 

1.  YTo    g'^^i'^   of  strychnine  yields  a   very  copious,   bright  yellow 

deposit,  which  after  a  time  disappears,  but  it  is  reproduced 
upon  further  addition  of  the  reagent. 

2.  YFoT  gr^^i^  yields  a  copious  precipitate. 

3.  Yo'.oTo'  grain  :  a  very  good  deposit. 

4.  -g-Q-.^-oT  gi^ain  yields  a  very  satisfactory,  yellow  precipitate. 

5.  yotVfo   grain  yields  a  distinct  turbidity,  which  after  a  time  dis- 

appears, and  is  not  reproduced  upon  further  addition  of  the 
reagent. 
The   reaction  of  this   reagent   is  common  to  a   large  class  of 
organic  substances. 

14.  Physiological  Test. 

Dr.  Marshall  Hall  proposed  to  take  advantage  of  the  extreme 
sensibility  of  frogs  to  the  effects  of  strychnine  as  a  means  of  detect- 
ing its  presence.  He  advised  to  immerse  the  frog  in  a  solution  of 
the  poison  ;  when  sooner  or  later,  according  to  the  strength  of  the 
solution,  the  animal  is  seized  with  violent  tetanic  convulsions,  in 
which  the  extremities  become  extended  to  their  uttermost  and  the 
whole  body  perfectly  rigid.  By  this  method  Dr.  Hall  states  that 
he  was  enabled  to  detect  l-5000th  of  a  grain  of  strychnine.  More 
recently  Dr.  Harley  proposed  to  inject  the  strychnine  solution  into 
the  thoracic  or  abdominal  cavity  of  the  animal ;  and  he  states  that 
1— 16,000th  of  a  grain  of  strychnine  acetate  introduced  into  the 
lungs  of  a  very  small  frog  will  render  it  violently  tetanic  in  about 
ten  minutes. 

In  the  following  examinations  of  this  test,  about  two  grains  of 
the  strychnine  solution  were  taken  up  by  a  pipette,  the  filled  end  of 


PirYSIOT.OOIPAI^    TKST.  585 

whicli  was  (hen  iiitnitliiccd  into  the  stomiu^li  of  the  frooj,  and  the 
liqiiul  (lischari^ed  by  blowing  through  tlie  tube.  The  animals  were 
then  placed  under  an  open  glass  receiver.  The  frogs  were  fresh, 
and  varied  in  weight  from  fifteen  to  fifty  grains.  The  results  for 
each  quantity  of  the  poison  are  based  upon  numerous  exj)eriments, 
and  chiedy  upon  the  species  of  animal  known  as  Rana  Ilalecina. 

1.  1-lOOth  solution — equal  to  about  l-50th  grain  of  strychnine — 

usually  produces  immediate  and  violent  spasms,  and  death  in 
about  eight  minutes. 

2.  1-1 000th  solution  :  the  symptoms  generally  manifest  themselves 

in  three  or  four  minutes,  and  death  usually  takes  place  in  from 
fifteen  to  thirty  minutes. 

3.  l-10,000th  solution:  in  some  instances  the  symptoms  appeared 

within  ten  minutes,  while  in  others  they  were  delayed  as  long 
as  half  an  hour. 

4.  l-20,000th  solution  generally  produces  characteristic  symptoms 

in  from  thirty  to  forty-five  minutes;  but  in  some  few  instances 
the  results  were  not  well  marked,  even  after  long  periods. 

5.  l-30,000th  solution,  or  l-15,000th  grain  of  strychnine  :  in  most 

instances,  especially  when  very  small  animals  were  employed, 
the  symptoms  appeared  within  fifty  minutes  ;  but  in  some  cases 
there  were  no  marked  effects,  even  after  some  hours. 

In  applying  this  test,  the  frogs  should  always  be  fresh  from  the 
pond.  Occasional  agitation  of  the  animal  hastens  the  action  of  the 
smaller  quantities  of  the  poison  ;  and  frequently  a  violent  paroxysm 
may  be  induced  by  a  sudden  noise,  such  as  clapping  of  the  hands. 
From  experiments  made  at  different  times,  we  are  strongly  inclined 
to  believe  that  the  sensibility  of  this  animal  to  the  effects  of  strych- 
nine differs  somewhat  with  the  seasons  of  the  year.  The  spring 
and  early  part  of  the  summer  seem  to  be  the  most  favorable  for  the 
application  of  the  test.  It  may  be  remarked  that,  in  regard  to 
weight,  l-20,000th  of  a  grain  of  strychnine  bears  about  the  same 
relation  to  a  frog  weighing  twenty-five  grains  that  two  grains  do  to 
a  man  weighing  one  hundred  and  forty  pounds.  When,  therefore, 
the  foregoing  experiments  are  taken  in  connection  with  the  known 
effects  of  strychnine  upon  the  human  subject,  it  would  appear  that 
the  frog  is  relatively  somewhat  less  sensitive  than  man  to  the 
action  of  the  poison. 

This  physiological  test  certainly  affords  a  very  valuable  means  of 


586  STRYCHNINE. 

corroborating  the  chemical  evidence  of  the  presence  of  strychnine, 
and  at  the  same  time,  as  we  have  just  seen,  it  is  extremely  delicate; 
yet  it  should  never  be  employed  to  the  exclusion  of  at  least  some  of 
the  chemical  tests.  In  regard  to  delicacy  of  action,  for  the  pure 
alkaloid,  it  is  much  inferior  to  the  color  test,  the  latter  yielding 
satisfactory  results  with  a  quantity  of  the  poison  that  would  produce 
no  appreciable  effect  upon  a  frog,  even  of  the  smallest  size. 

Other  Reagents. —  Chlorine  gas  passed  into  somewhat  strong  solu- 
tions of  salts  of  strychnine  produces  a  white,  amorphous  precipitate. 
Ten  grains  of  a  1-1 000th  solution  of  the  alkaloid  yield  a  quite  good 
deposit,  which  is  unchanged  upon  the  addition  of  ammonia ;  a  similar 
quantity  of  a  1-10, 000th  solution  yields  a  distinct  milkiness,  which 
quickly  disappears  on  the  addition  of  ammonia. 

Tannic  add,  jphosphomolyhdie  acid,  phosphoantimonic  acid,  meta- 
tungstic  acid,  and  Nessler's  test  for  ammonia  also  precipitate  strych- 
nine from  solutions  of  its  salts,  even  in  some  instances  when  very 
highly  diluted.  But,  as  the  reactions  of  these  reagents  are  common 
to  a  large  class  of  organic  compounds,  the  results  have  little  or  no 
positive  value.  Gallic  acid  fails  to  produce  a  precipitate,  even  in 
highly  concentrated  solutions  of  salts  of  strychnine. 

Separation  from  Organic  Mixtures. 

From  Nux  Vomica. — Strychnine  may  be  separated  from  powdered 
nux  vomica  by  digesting  the  powder  for  some  time  at  a  moderate 
heat  with  a  small  quantity  of  water  slightly  acidulated  with  acetic 
acid ;  the  cooled  liquid  is  filtered,  and  the  filtrate  concentrated  over 
a  water-bath  to  a  small  volume.  The  concentrated  solution,  which 
will  have  the  intensely  bitter  taste  of  the  alkaloid,  is  treated  with 
slight  excess  of  potassium  or  sodium  hydrate,  and  violently  agitated 
with  about  its  own  volume  of  chloroform.  After  the  liquids  have 
completely  separated,  the  chloroform  is  carefully  withdrawn  and 
allowed  to  evaporate  spontaneously  in  a  watch-glass,  when  the  alka- 
loid will  be  left  usually  in  its  amorphous  state,  together  with  more 
or  less  foreign  matter. 

The  residue  thus  obtained  may  either  be  examined  at  once  by  the 
chemical  tests  for  strychnine,  or  be  further  purified  by  dissolving  it 
in  a  very  small  quantity  of  acidulated  water,  rendering  the  solution 
alkaline,  and  again  extracting  with  chloroform.     After  examining  a 


SEPARATION    FROM    ORGANIC    MIXTURES.  587 

portion  of  the  residue  by  the  color  test,  any  reniaininj^  portion  may 
be  (lissolveil  in  a  small  quantity  of  water  containing  a  trace  of  acetic 
acid,  and  the  solution  tested  by  potassium  dichromate,  or  any  of  the 
other  liquid  tests  for  the  alkaloid. 

A  single  grain  of  powdered  nux  vomica,  when  treated  after  the 
above  method,  will  yield  very  satisfactory  evidence  of  the  presence 
of  strychnine.  If  the  nux  vomica  or  vegetable  infusion  contains  a 
comparatively  large  proportion  of  hrucine,  this  may  interfere  with 
the  color  reaction  of  the  strychnine.  These  alkaloids  may  be  sepa- 
rated by  one  or  other  of  the  metliods  already  described. 

Suspected  Solutions  and  Contents  of  the  Stomach. — 
Any  organic  solids  present  in  the  mixture  presented  for  examination 
are  cut  into  small  pieces,  and  the  mass,  after  the  addition  of  water  if 
necessary,  treated  with  about  half  its  volume  of  strong  alcohol  and 
sufficient  acetic  acid  to  give  it  a  distinctly  acid  reaction.  The  acidu- 
lated mixture  is  digested  at  a  moderate  heat  on  a  water-buth,  with 
frequent  stirring,  for  about  half  an  hour  or  longer.  It  is  then,  after 
cooling,  thrown  upon  a  wet  linen  strainer,  and  the  solid  residue 
well  washed  with  diluted  alcohol  and  strongly  pressed.  The  mixed 
strained  fluids  are  concentrated  at  a  moderate  temperature  to  a  small 
volume,  again  strained,  then  filtered,  and  evaporated  on  a  water-bath 
to  about  dryness.  Any  strychnine  present  will  now  be  in  the  residue, 
in  the  form  of  acetate,  mixed  with  more  or  less  foreign  matter. 

The  residue  thus  obtained  is  thoroughly  stirred  with  a  small 
<juantity  of  water  containing  a  drop  of  acetic  acid,  the  liquid  filtered, 
the  filter  washed  with  a  little  water,  and  the  mixed  filtrates,  after 
concentration  if  necessary,  transferred  to  a  stout  test-tube  or  small 
bottle,  and  treated  with  slight  excess  of  a  caustic  alkali  or  its  car- 
bonate, when  the  strychnine  will  be  set  free  from  its  saline  combina- 
tion. Should  the  mixture  contain  a  comparatively  large  quantity  of 
the  alkaloid,  the  latter  may  after  a  time  assume  the  crystalline  form. 
The  alkaline  mixture  is  now  violently  agitated  for  some  little  time 
with  something  more  than  its  own  volume  of  pure  chloroform. 
When  the  liquids  have  fully  separated,  the  supernatant  aqueous  fluid 
is  transferred,  by  means  of  a  pipette,  to  another  test-tube,  and  the 
chloroform  decanted  into  a  glass  capsule  or  watch-glass,  care  being 
taken  that  no  remaining  drops  of  the  aqueous  liquid  pass  over  with 
the  chloroform  ;  the  alkaline  aqueous  mixture  is  then  washed  with 
-a  fresh  portion  of  chloroform,  and  this  collected  with   that  first  em- 


588  STEYCHNINE. 

ployed.  A  very  good  method  for  separating  the  last  drops  of  the 
aqueous  liquid  from  the  decanted  chloroform  is  to  collect  the  latter 
liquid  in  a  dry  test-tube  and  decant  it  from  this  into  the  capsule : 
the  last  traces  of  the  former  fluid  will  now  usually  remain  attached 
to  the  sides  of  the  tube.  If,  however,  the  chloroform  has  still  a 
milky  appearance,  the  liquid  may  be  passed  through  a  small  paper 
filter,  previously  moistened  with  pure  chloroform. 

The  decanted  chloroform,  which  contains  any  strychnine  that 
was  present  in  the  alkaline  mixture,  is  allowed  to  evaporate  sponta- 
neously to  dryness.  If  the  liquid  contained  a  very  notable  quantity 
of  the  alkaloid,  the  latter  may  remain  in  its  crystalline  form  :  this 
result,  however,  is  rarely  obtained  from  the  first  chloroform  extract, 
when  operating  on  the  contents  of  a  stomach  containing  the  poison. 
A  portion  of  the  residue  may  be  examined  by  the  color  test,  as  also 
by  the  taste ;  and  any  remaining  portion  dissolved  in  an  appropriate 
quantity  of  pure  water  containing  a  trace  of  acetic  acid,  and  the 
solution,  after  filtration  if  necessary,  examined  by  some  of  the  liquid 
tests  for  strychnine,  especially  potassium  dichromate.  If,  however, 
the  examination  of  a  small  portion  of  the  dry  residue  should  indicate 
the  presence  of  much  foreign  matter,  the  acidulated  aqueous  solu- 
tion is  rendered  alkaline,  and  again  extracted  by  chloroform,  which 
on  evaporation  may  leave  the  alkaloid,  even  when  present  only  in 
minute  quantity,  in  its  crystalline  state,  or  at  least  sufficiently  pure 
for  the  application  of  the  more  important  tests. 

On  agitating  the  prepared  alkaline  solution  with  chloroform,  it 
sometimes  happens  that  the  whole  becomes  a  frothy  emulsion,  from 
which  the  chloroform  will  not  separate,  even  after  several  hours. 
When  this  occurs,  the  mixture  may  be  moderately  agitated  with 
about  half  its  volume  of  pure  water,  and  the  whole  allowed  to  re- 
pose, if  necessary,  for  some  hours,  when  more  or  less  of  the  water 
will  separate  as  a  highly-colored  fluid  ;  this  is  decanted,  and  the 
operation  repeated  with  fresh  portions  of  water  so  long  as  the  liquid 
becomes  colored.  By  this  means  much  of  the  foreign  matter  will 
be  separated,  while  any  strychnine  present  will  remain  in  solution  in 
the  chloroform  mixture,  at  most  only  the  merest  trace  of  it  being 
taken  up  by  the  decanted  water.  The  mixture  is  now  slightly  acidu- 
lated by  acetic  acid,  then  transferred  to  a  small  dish,  and  evaporated 
to  dryness  on  a  water-bath;  the  residue  is  stirred  with  a  very  small 
quantity  of  pure  water,  the  solution,   after  filtration  if  necessary, 


SKPARATION    VllOM    OIJOANK."    MIXTURES.  580 

rendered  sliu;li(lv  alkaline,  and  a<:;ain  au^italed  with  fresh  chloroforin, 
whieh  will  now  nsnally  readily  separate.  Instead  of  treatinj^  the 
aeidnlated  ehloroforni  mixture  in  the  manner  just  described,  it  may 
be  a«)jitated  with  consecutive  portions  of  pure  water  as  long  as  this 
liquid  acquires  a  bitter  taste,  when  the  alkaloid  will  be  extracted  as 
strychnine  acetate,  and  be  left  as  such  on  evaporating  the  solution  to 
dryness  over  a  water-bath. 

On  applying  the  general  method  now  described  to  the  examina- 
tion ol'  the  contents  of  the  stomaciis  of  several  dillerent  cats,  each  of 
which  had  been  killed  by  half  a  grain  of  strychnine,  we  in  every 
instance  recovered  a  very  notable  quantity  of  the  poison.  Tiie  only 
instance  in  which  a  quantitative  analysis  was  made  was  in  the  case 
of  a  young  cat,  to  which  the  strychnine  had  been  administered  in 
solution  upon  a  very  full  stomach,  and  death  ensued  in  ten  minutes; 
the  third  chloroform  extract  furnished  11-lOOths  of  a  grain  of  the 
crystallized  alkaloid. 

After  the  same  method,  from  the  contents  of  the  stomach  of  a 
man  wlio  liad  died  from  the  effects  of  strychnine,  administered, 
there  is  every  reason  for  believing,  in  comparatively  small  quantity, 
18-lOOths  of  a  grain  of  the  alkaloid,  chiefly  in  its  crystalline  state, 
was  recovered.  And  in  another  case,  in  which  an  unknown  quantity 
of  the  poison  had  been  administered  and  death  took  place  in  about 
an  hour,  31-lOOths  of  a  grain  was  obtained. 

When  the  chloroform  or  ether  residue  contains  a  comparatively 
large  quantity  of  foreign  organic  matter,  it  may  fail  to  res|)ond  to  the 
color  test  for  strychnine,  even  wdien  a  very  notable  quantity  of  the 
alkaloid  is  present,  and  the  residue  has  an  intensely  bitter  taste. 
Under  these  circumstances,  the  residue  may  be  treated  with  a  few 
drops  of  pure  concentrated  sulphuric  acid,  and  heated  on  a  water- 
bath  at  100°  C.  (212°  F.)  for  some  hours,  by  which  the  foreign 
matter  will  be  more  or  less  charred.  To  the  cooled  mixture  pulver- 
ized barium  carbonate  is  added  in  quantity  sufficient  to  very  nearly,  but 
710^  fully,  neutralize  the  acid ;  the  mixture  is  now  thoroughly  stirred 
with  a  little  water,  the  liquid  filtered,  then  rendered  alkaline,  and  the 
strychnine  extracted  with  chloroform  or  ether  in  the  usual  manner. 

After  this  method  we  have  recovered  the  alkaloid,  in  its  nearly 
pure  state,  from  a  mixture  of  1-lOOOth  grain  of  strychnine  with  one 
grain  of  animal  extractive  matter.  Under  the  action  of  concen- 
trated sulphuric  acid  at  150°  C.  (302°  F.),  in  the  presence  of  organic 


590  STRYCHXIXE. 

matter,  strychnine  may  undergo  decomposition;  Nordhausen sulphuric 
acid  decomposes  it  at  100°  C. 

Method  hy  Dialysis. — To  apply  this  process,  the  details  of  which 
have  heretofore  been  pointed  out  {ante,  p.  427),  the  organic  mixture, 
acidulated  with  acetic  or  hydrochloric  acid,  is  prepared  in  the  manner 
already  described  for  the  examination  of  the  contents  of  the  stomach, 
and  the  concentrated  solution  placed  in  the  dialyzer,  which  is  then 
floated  in  a  dish  containing  four  or  five  times  as  much  pure  water  as 
the  volume  of  fluid  to  be  dialyzed ;  after  twenty-four  or  thirty-six 
hours,  the  diffusate  is  transferred  to  a  porcelain  dish,  evaporated  to 
dryness  on  a  water-bath,  and  the  residue  examined  in  the  ordinary 
manner. 

In  regard  to  the  relative  merits  of  this  method,  even  with  mix- 
tures containing  comparatively  large  quantities  of  strychnine,  ex- 
periments indicate  that  the  difusate  usually  becomes  contaminated 
to  such  an  extent  with  foreign  matter,  that  to  separate  the  alkaloid 
from  this  requires  just  the  same  operations  as  are  required  to  recover 
it  directly  by  the  ordinary  methods  from  the  original  mixture ;  more- 
over, the  relative  quantity  of  the  alkaloid  that  passes  into  the  difiu- 
sate,  even  after  twenty-four  or  thirty-six  hours,  never  exceeds  the 
proportion  existing  between  the  volume  of  liqaid  in  the  diffusate 
aud  that  in  the  dialyzer.  The  results  of  many  experiments  might 
be  cited  in  support  of  the  foregoing  statements,  (See  1st  edition 
Micro- Chemistry  of  Poisons,  583.) 

Fhom  the  Tissues. — For  the  recovery  of  absorbed  strychnine, 
the  soft  organ,  such  as  a  portion  of  the  liver,  is  placed  in  a  porcelain 
evaporating-dish  and  cut  into  very  small  pieces,  taking  care  that 
none  of  the  fluid  present  is  lost ;  the  mass  is  rendered  sufficiently 
liquid  by  water,  some  strong  alcohol  added,  and  the  whole  well 
stirred,  and  acidulated  with  sulphuric  acid,  in  the  proportion  of 
about  eight  drops  of  the  concentrated  acid  for  each  fluid-ounce  of 
the  mixture.  It  is  then  digested  at  a  temperature  of  about  82°  C. 
(180°  F.),  with  frequent  stirring,  for  half  an  hour  or  longer,  and, 
after  cooling,  strained  through  a  fine  linen  cloth,  the  residue  washed 
with  acidulated  water  and  strongly  pressed. 

The  strained  liquid,  including  the  washings,  thus  obtained  is 
concentrated  on  a  water- bath,  and,  when  much  solid  matter  has 
separated,  again  strained,  these  operations  being  repeated  until  the 
fluid  is  reduced  to  a  small  volume.     This  is  nearly  neutralized  with 


SEPARATION    FROM    TIIK   TISSUES.  591 

a  fixed  caustic  alkali  or  ammonia,  takii)<r  care,  however,  that  the 
mixture  still  retains  a  very  decided  acid  reaction  ;  then  filtered,  and 
the  filtrate  evaporated,  on  a  water-bath,  until  only  a  few  drops  of 
liquid  remain.  When  this  residue  has  cooled,  it  is  well  stirred  with 
about  half  an  ounce  of  strong  alcohol,  wiiicii  will  dissolve,  in  the 
form  of  sulphate,  any  strychnine  present,  while  the  alkali-sulphate, 
formed  from  the  sulphuric  acid  and  alkali  added,  together  with  more 
or  less  of  the  foreign  organic  matter,  will  remain  undissolved.  The 
alcoholic  solution,  after  filtration,  is  evaporated  on  a  water-bath  to 
almost  dryness,  the  residue  stirred  with  a  small  quantity  of  pure 
water,  and  the  filtered  solution  rendered  slightly  alkaline.  It  is 
then  agitated  with  pure  chloroform  in  the  usual  manner,  and  this 
fluid,  after  careful  separation,  allowed  to  evaporate  spontaneously. 

If  on  stirring  the  above  nearly  dry  residue  with  strong  alcohol, 
for  the  separation  of  the  strychnine  from  the  alkali-salt,  it  should 
form  a  tenacious  gummy  mass  that  will  not  mix  with  the  liquid, — as 
is  sometimes  the  case,  especially  when  the  subject  under  examination 
is  the  liver, — the  fluid  is  exi)elled  by  evaporation,  the  residue  stirred 
with  water,  the  filtered  solution  evaporated  to  nearly  dryness,  and 
the  residue  again  treated  with  alcohol,  with  which  the  deposit  will 
now  usually  readily  mix.  Again,  should  the  final  al4caline  solution, 
when  agitated  with  chloroform,  form  an  emulsion  from  which  the 
chloroform  will  not  separate,  the  mixture  is  treated  after  one  or  other 
of  the  methods  before  described  for  mixtures  of  this  kind.  So,  also, 
should  the  final  chloroform  residue  contain  much  foreign  organic 
matter,  this  may  be  charred  by  concentrated  sulphuric  acid  at  100° 
C.  in  the  manner  already  directed  {ante,  589). 

The  sixth  of  a  grain  of  strychnine,  in  solution,  was  given  to  a 
healthy  cat,  which  had  just  been  fed.  Twelve  minutes  thereafter, 
the  animal  was  seized  with  violent  tetanic  sym])toms,  and  died  three 
minutes  later.  The  liver,  together  with  the  contained  blood,  was 
then  treated  after  the  preceding  method.  The  first  chloroform  solu- 
tion thus  obtained  left  on  spontaneous  evaporation  a  very  small 
gummy  residue,  which,  when  examined  in  three  separate  portions  by 
the  color  test,  gave,  in  each  instance,  perfectly  satisfactory  evidence 
of  the  presence  of  strychnine.  Although  the  quantity  of  the  poison 
thus  recovered  was  even  more  than  sufficient  to  establish  fully  its 
presence  by  this  test,  yet  it  was,  probably,  too  minute  to  have  j)er- 
mitted  the  reaction  of  this  test  being  confirmed  by  any  of  the  other 


592  STEYCHXINE. 

tests,  except  by  the  taste.  Whether  the  strychnine  recovered  in  this 
instance  was  simply  present  in  the  blood  contained  in  the  liver,  or 
whether  a  portion  of  it  had  been  deposited  in  the  tissue  of  this 
organ,  is  difficult  to  decide.  None  of  the  other  tissues  of  this  animal 
were  examined.  An  analysis  of  the  gall-bladder  and  its  contents 
of  a  similar  animal,  killed  in  fifteen  minutes  by  the  sixth  of  a  grain 
of  strychnine,  failed  to  reveal  the  presence  of  a  trace  of  the  poison. 

In  a  case  of  suspected  poisoning  by  strychnine,  in  which  the  person 
died  in  forty  minutes  under  violent  tetanic  convulsions,  one  hundred 
and  fifty  grammes  (nearly  five  ounces)  of  the  liver  were  preserved  in 
alcohol  for  three  months.  The  finely-divided  tissue,  with  the  alco- 
hol, was  then  examined  after  the  foregoing  method,  the  chloroform 
residue  being  charred  with  sulphuric  acid.  The  final  residue  had  a 
yellowish  color,  was  amorphous,  and  weighed  6-lOOths  of  a  grain. 
Under  the  action  of  the  color  test,  about  the  least  visible  portion  of 
the  residue  gave  perfectly  satisfactory  evidence  of  the  presence  of 
strychnine,  the  reaction  being  about  as  well  marked  as  with  the  pure 
alkaloid. 

For  the  recovery  of  strychnine  from  complex  organic  mixtures 
and  the  tissues,  Dr.  Th.  Chandelon  has  recently  advised  {Zeits.  /. 
Physiol.  Chem.,  Nov.  1884,  40)  the  following  method. 

The  concentrated  organic  mixture  or  the  finely-divided  tissue  is 
mixed  with  an  equal  weight  of  perfectly  anhydrous  gypsum,  obtained 
by  heating  commercial  calcium  sulphate  in  a  current  of  dry  air  at 
130°  C.  (266°  F.)  until  a  portion,  on  being  mixed  with  water, 
becomes  solid.  The  gypsum  mixture  is  thoroughly  triturated  in  a 
mortar,  and  allowed  to  stand  four  or  five  hours,  or  until  the  mags 
becomes  so  solid  that  it  may  be  broken  into  small  fragments.  These 
are  placed  in  a  flat  porcelain  dish  on  a  water-bath  or  in  a  drying- 
oven,  and  dried  at  70°  C.  (158°  F.).  The  dried  lumps  are  pul- 
verized, and  the  powder  treated  with  90  per  cent,  alcohol  to  which 
one  gramme  of  tartaric  acid  has  been  added  for  every  one  hundred 
grammes  of  fresh  animal  tissue  present. 

The  alcoholic  mixture  is  boiled  for  a  few  hours  in  a  flask  pro- 
vided with  a  condenser  to  return  the  alcohol ;  the  cooled  liquid  is 
filtered,  and  the  solid  residue  washed  with  fresh  hot  alcohol,  this 
being  collected  with  the  first  filtrate.  The  alcoholic  liquid,  which 
should  be  distinctly  acid,  is  distilled  in  a  flask  until  the  principal 
portion  of  the  alcohol  has  been  expelled,  after  which  the  mixture  is 


RECOVERY    FROM    THE    lU.OOl).  593 

evaporated  to  dryness  on  a  water-batli.  The  residue  is  treated  with 
a  little  hoiliiii"-  water,  and  the  mixture  allowed  to  cool,  so  that  any 
fatty  matter  j)resent  may  separate.  The  filtered  liquid  is  concen- 
trated to  about  20  c.c,  then  rendered  alkaline  by  sodium  hydrate, 
and  mixed  on  a  large  wateh-olass  with  sufficieiit  <i;ypsum  to  render 
the  whole  solid.  The  pulverized  mass  is  dried  in  a  sulphuric  acid 
desiccator,  and  finally  extracted  with  pure  chloroform  in  a  Soxhlet 
a])paratus  of  large  size. 

The  decanted  chloroform  is  concentrated  to  10  or  15  c.c,  and, 
if  necessary,  filtered.  It  is  then  treated  with  an  equal  volume  of  a 
saturated  ethereal  solution  of  oxalic  acid.  Crystalline  needles  and 
tufts  of  the  oxalate  of  strychnine  will  quickly  appear,  and  in  a  little 
time  the  whole  of  the  alkaloid  will  be  thus  precipitated.  The  strych- 
nine oxalate  is  collected  on  a  filter,  washed  with  a  mixture  of  equal 
volumes  of  chloroform  and  ether,  and  dried.  It  is  then  dissolved 
in  about  the  least  possible  quantity  of  water,  and  the  solution  treated 
with  slight  excess  of  ammonia,  when  the  strychnine,  in  its  pure  state, 
will  be  precipitated  in  the  form  of  crystalline  needles. 

On  applying  this  method  for  the  recovery  of  strychnine  in 
experiments  upon  a  frog  and  a  rabbit,  killed  by  the  subcutaneous 
injection  respectively  of  ten  and  forty  milligrammes  of  the  alkaloid. 
Dr.  Chandelon  obtained  very  satisfactory  results.  So,  also,  in  some 
quantitative  experiments  in  which  small  portions  of  strychnine  were 
added  to  large  quantities  of  animal  tissue,  very  nearly  the  whole  of 
the  alkaloid  was  recovered. 

The  Blood. — This  fluid  may  be  examined  for  absorbed  strych- 
nine in  much  the  same  manner  as  heretofore  described  for  the  anal- 
ysis of  the  tissues.  About  four  fluid-ounces  of  the  suspected  blood, 
placed  in  a  flask,  are  treated  with  an  equal  volume  of  water  and 
about  half  a  volume  of  strong  alcohol,  then  about  eight  minims 
of  concentrated  sulphuric  acid  added  for  each  ounce  of  blood,  and 
the  whole  thoroughly  agitated  until  the  mixture  becomes  perfectly 
homofireueous.  It  is  then  transferred  to  a  dish  and  heated  on  a 
water-bath  to  near  the  boiling  temperature,  with  constant  stirring, 
for  about  fifteen  minutes;  while  still  warm,  the  liquid  portion  is 
squeezed  through  a  fine  linen  cloth,  and  the  black  viscid  residue 
washed  with  alcohol  and  pressed.  Should  the  whole  of  the  mixture 
pass  through  the  strainer,  as  will  be  the  case  if  too  nuich  acid  has 
been  added,  it  is  returned  to  the  dish,  treated  with  a  few  drops  of 

38 


594  STRYCHNINE. 

an  alkali,  and  again  heated  for  a  few  minutes,  then  strained.  If, 
on  the  other  hand,  the  solid  matter  separated  by  the  strainer,  when 
pressed,  is  dry  and  pulverizable,  it  is  returned  to  the  strained  liquid, 
the  mixture  heated  with  a  few  drops  more  of  sulphuric  acid,  and 
again  returned  to  the  strainer. 

The  highly  colored,  turbid  liquid  thus  obtained  is  now  partially 
neutralized  with  an  alkali,  concentrated  somewhat,  and  again  strained ; 
then  very  nearly  neutralized  with  the  alkali,  and  again  heated,  when 
most  of  the  albuminous  matter  will  separate  in  the  form  of  brownish 
flakes.  These  are  separated  by  a  linen  strainer,  washed  with  diluted 
alcohol,  and  strongly  pressed.  The  liquid,  which  will  now  usually 
have  only  a  light  brownish  color,  is  concentrated  on  a  water-bath 
to  a  small  volume,  filtered,  and  evaporated  to  near  dryness.  The 
residue  is  well  stirred  with  about  an  ounce  of  strong  alcohol,  the 
liquid  filtered,  and  the  solids  washed  with  diluted  alcohol.  The  al- 
coholic liquid  is  evaporated  to  near  dryness,  the  residue  thoroughly 
stirred  with  a  small  quantity  of  pure  water,  the  liquid  filtered,  then 
rendered  alkaline  and  extracted  with  chloroform  in  the  usual  manner. 
In  testing  the  final  residue,  it  should  be  remembered  that  at  most 
there  is  only  a  very  minute  quantity  of  strychnine  present. 

Absorbed  strychnine  seems  to  adhere  more  tenaciously  to  the 
solids  of  the  blood  than  any  of  the  other  ordinary  alkaloids,  with 
perhaps  the  single  exception  of  morphine.  For  its  recovery  from 
this  fluid,  it  is  essential  that  the  liquid,  after  the  addition  of  water 
and  alcohol,  be  at  first  acidulated  as  strongly  as  possible  compatible 
with  the  separation  of  at  least  a  portion  of  the  solid  matter.  The 
exact  quantity  of  acid  necessary  for  this  purpose  v/ill  vary  somewhat 
with  different  samples  of  blood ;  it  also  appears  that  sulphuric  acid 
is  better  adapted  than  any  other  acid  for  this  purpose.  If  the  poi- 
soned blood  be  acidulated  only  moderately,  as  for  the  recovery  of 
most  of  the  other  alkaloids,  the  whole  of  the  strychnine  will  usually 
be  separated  along  with  the  solid  albuminous  matter.  Before  resort- 
ing to  the  method  just  described,  we  had  followed  various  methods 
for  the  examination  of  the  blood  of  not  less  than  fifteen  difi'erent 
animals  killed  by  strychnine,  without  in  any  instance  obtaining 
distinct  evidence  of  the  presence  of  the  poison. 

On  applying  this  method  for  the  examination  of  the  blood  of 
six  different  cats  and  of  two  dogs,  poisoned  by  comparatively  small 
doses  of  strychnine,  we  in  every  instance  obtained  perfectly  satisfac- 


RECOVERY   FROM   THE   IJI.OOI).  595 

torv  evidence  of"  the  presence  of  the  alkaloid.  Jn  two  of  these  cases, 
in  eacli  of  which  Imlf  a  grain  of  strvclinine  had  been  administered 
to  younp;  oats  and  death  took  place  in  three  and  six  minutes  respec- 
tively, six  fluid-drachms  of  blood  from  each — the  whole  that  was 
obtained — Curnished  residues,  about  flu!  fifth  j)art  of  each  of  which, 
when  examined  by  the  color  test,  gave  un(}uestionable  evidence  of 
the  presence  of  the  alkaloid.  These  instances  show  the  extreme 
rapidity  witli  which  a  (juite  notable  quantity  of  the  poison  may  be 
absorbed.  In  fact,  in  these  two  cases  there  was  apparently  as  much 
strychnine  recovered  as  in  those  in  which  life  was  prolonged  for 
about  half  an  hour. 

In  none  of  these  experiments  did  the  chloroform  leave  the  strych- 
nine in  its  crystalline  state.  But  in  one  of  them,  after  the  presence 
of  the  poison  had  been  shown  in  a  portion  of  the  residue  by  the  color 
test,  the  remaining  portion,  when  stirred  with  a  drop  of  a  very  dilute 
solution  of  potassium  dichromate  and  the  fluid  allowed  to  evaporate 
spontaneously,  furnished  a  number  of  octahedral  crystals  of  the  chro- 
mate  of  strychnine :  this  was  the  only  instance  in  which  the  residue 
was  thus  treated.  In  every  instance  the  whole  of  the  blood  that 
could  be  obtained  from  the  animal  was  examined  at  one  operation. 
It  does  not,  of  course,  follow  that  a  given  quantify  of  blood  taken 
from  the  human  subject,  poisoned  by  strychnine,  would  contain  the 
same  amount  of  the  poison  as  would  be  present,  under  like  condi- 
tions, in  a  similar  quantity  of  blood  from  a  cat.  Indeed,  the  differ- 
ence between  the  smallest  fatal  dose  for  the  former  and  that  for 
the  latter  seems  to  be  very  much  less  than  that  between  the  absolute 
quantities  of  blood  found  in  each. 

In  a  case  of  poisoning  in  the  human  subject,  in  which  we  re- 
covered 14-lOOths  of  a  grain  of  strychnine  from  the  contents  of  the 
stomach,  about  two  ounces  of  blood,  examined  after  the  above 
method,  furnished  satisfactory  evidence  of  the  presence  of  the  alka- 
loid. In  this  instance,  the  patient  being  a  man,  death  took  place  in 
about  half  an  hour  after  the  poison  had  been  taken. 

On  following  the  method  of  Dialysis,  in  three  different  cases, 
for  the  examination  of  the  blood  of  animals  poisoned  by  strychnine, 
we  in  no  instance  detected  a  trace  of  the  poison  in  the  diffusate. 
Previously  to  introducing  the  blood  into  the  dialyzer,  the  stronglv 
acidulated  fluid  was  heated  for  some  time  with  diluted  alcohol,  then 
strained  and  concentrated.    On  examining  the  dialyzed  blood,  in  one 


596  STRYCHNINE. 

case,  by  the  method  heretofore  described,  it  furnished  very  distinct 
evidence  of  the  presence  of  strychnine. 

From  the  Ueine. — Strychnine  may  be  separated  from  the 
urine  by  acidulating  the  liquid  with  a  few  drops  of  acetic  acid,  and 
evaporating  it  on  a  water-bath  to  a  thick  syrup.  When  this  has 
cooled,  it  is  well  stirred  with  about  a  fluid-ounce,  of  nearly  absolute 
alcohol,  the  liquid  filtered,  and  the  residue  on  the  filter  washed  with 
similar  alcohol,  and  then  strongly  pressed.  The  yellowish  filtrate 
thus  obtained  is  concentrated  to  a  thick  syrup,  and  the  residue  dis- 
solved in  a  small  quantity  of  pure  water.  This  solution,  after  fil- 
tration if  necessary,  is  rendered  slightly  alkaline,  by  ammonia  or 
either  of  the  fixed  alkalies,  and  agitated  in  the  ordinary  manner  with 
pure  chloroform,  which,  after  separation,  is  allowed  to  evaporate 
spontaneously,  when  the  alkaloid,  if  present  in  very  notable  quantity, 
will  be  left  in  its  crystalline  state. 

By  following  this  method  for  the  examination  of  a  fluid-ounce 
of  normal  urine,  to  which  the  1-lOOth  of  a  grain  of  strychnine  has 
been  purposely  added, — the  dilution  being  one  part  of  the  poison  in 
about  50,000  parts  of  liquid, — the  alkaloid  may  be  recovered,  in 
its  crystalline  form,  with  scarcely  any  appreciable  loss. 

One-fourth  of  a  grain  of  strychnine,  in  solution,  was  given  to  a 
very  large  dog,  weighing  about  eighty-five  pounds.  Slight  tetanic 
symptoms  manifested  themselves  in  about  fifteen  minutes.  These 
continued  for  about  a  quarter  of  an  hour,  when  a  second  dose,  con- 
taining a  similar  quantity  of  the  poison,  was  administered.  The 
animal  was  now  soon  seized  with  violent  symptoms,  but  survived 
the  efi^ects  of  the  poison  one  hour  and  three-quarters  after  the  ad- 
ministration of  the  first  dose.  Five  ounces  of  urine  were  recovered 
from  the  bladder,  and  treated  after  the  foregoing  method ;  but  the 
examination  failed  to  reveal  any  distinct  evidence  of  the  presence  of 
the  alkaloid.  A  second  dog,  weighing  about  sixty  pounds,  was  given 
a  quarter  of  a  grain  of  the  acetate  of  strychnine.  Symptoms  ap- 
peared in  twenty  minutes,  and  after  twenty  minutes  more  the  ani- 
mal was  found  dead.  An  examination  of  five  and  a  half  ounces  of 
urine  obtained  from  this  animal  also  failed  to  indicate  the  presence 
of  strychnine.  In  this  case  the  urine  was  strongly  acidulated  with 
sulphuric  acid,  instead  of  acetic  acid,  as  in  the  preceding  exami- 
nations. In  an  instance,  however,  in  which  the  above  method  was 
employed  for  the  examination  of  two  ounces  of  bloody  urine  obtained , 


FAILURE   TO    DKTKCT.  597 

iVom  (he  l)l;ul(ler  of  a  man  who  had  (lic<l  in  otic  hour  and  three- 
quarters  from  the  elVeets  of  an  unknown  quantity  of  .strychnine, 
the  second  chloroform  residue,  when  examined  by  the  color  test, 
gave  satisf\ictory  evidence  of  the  presence  of  the  alkaloid.  Accord- 
ing to  G.  A.  Masing,  in  acute  strychnine  jjoisoning  the  urine  inva- 
riably yields  negative  results,  but  in  chronic  cases  the  alkaloid  may 
sometimes  be  found  in  this  secretion. 

Failure  to  detect  the  Poison. — It  has  not  unfrequently 
haj^pened,  in  fatal  poisoning  by  strychnine,  that  there  was  a  failure 
to  detect  a  trace  of  the  poison,  even  in  the  contents  of  the  stomach 
and  under  circumstances  apparently  very  favorable  for  its  recovery. 
There  is  little  doubt  that  some  of  these  failures  may  be  justly  attrib- 
uted to  the  imperfect  methods  of  analysis  employed  ;  yet  they  liave 
occurred  in  the  hands  of  the  most  experienced  manipulators.  The 
whole  of  the  poison  may  be  rapidly  removed  from  the  stomach  by 
the  process  of  absorption  or  the  act  of  vomiting,  or  by  these  com- 
bined ;  and,  in  protracted  cases,  even  that  which  has  been  absorbed 
may  be  entirely  eliminated  from  the  body  previous  to  death. 

In  a  case  related  by  Dr.  Taylor  {Poisoning  by  Strychnia,  151), 
in  which  five  grains  of  strychnine,  administered  by  mistake  to  a 
lady,  proved  speedily  fatal,  not  a  trace  of  the  pOison  was  found  in 
the  contents  of  the  stomach.  And  in  a  more  recent  case,  in  which  an 
infant  two  days  old  was  killed  in  two  hours  by  a  teaspoonful  of  nux 
vomica,  Prof.  Hofraann  failed  to  find  a  trace  of  strychnine,  either 
in  the  stomach,  intestines,  or  liver.  (Amer.  Jour.  Med.  Sci.,  April, 
1879,  574.)  In  an  instance  in  which  six  grains  of  strychnine  had 
been  taken.  Prof.  Sonnenschein  found  a  quantity  of  the  alkaloid  in 
the  stomach ;  but  none  was  recovered  from  either  the  tissues  or  the 
blood. 

In  the  case  reported  by  Dr.  J.  J.  Reese,  already  cited,  in  which 
about  six  grains  of  strychnine  had  been  taken  and  life  was  prolonged 
for  six  hours,  separate  analyses,  made  eight  loeehs  after  death,  of  the 
contents  of  the  stomach,  of  the  contents  of  the  small  intestines, 
and  of  the  tissues  of  the  stomach  and  intestines,  failed  to  reveal  the 
presence  of  a  trace  of  strychnine,  either  by  the  taste  of  the  final 
extract  or  by  the  color  test.  From  the  quantity  of  strychnine  taken 
in  this  instance,  and  the  fact  that  there  seems  to  have  been  no  vomit- 
ing, it  was  one  apparently  favorable  for  the  recovery  of  the  poison, 
especially  as  the  tissues  were  in  a  good  state  of  preservation  at  the 


598  STRYCHNINE. 

time  of  the  examination.  Dr.  Reese  attributed  the  faihire  to  the 
fact  that  just  before  death  the  deceased  had  taken  a  quarter  of  a 
grain  of  morphine,  which,  as  we  have  ah'eady  seen,  has  the  property 
of  disguising  the  ordinary  reaction  of  the  color  test.  But,  as  the 
final  extracts  were  obtained  through  the  agency  of  ether,  in  which 
morphine  is  almost  wholly  insoluble,  especially  in  the  presence  of  a 
free  alkali,  this  explanation  can  hardly  be  admitted  ;  moreover, 
morphine  has  not  the  property  of  concealing  the  intensely  bitter 
taste  of  strychnine. 

A  veterinary  surgeon  of  Bavaria  was  accused  of  poisoning  his 
wife  with  strychnine,  she  having  died  under  violent  tetanic  con- 
vulsions in  two  hours  after  he  had  given  her  a  "  purgative  medi- 
cine." A  chemical  examination  for  strychnine,  by  Prof.  Buchner, 
of  Munich,  of  the  internal  organs,  removed  from  the  corpse  four 
months  after  burial,  furnished  absolutely  negative  results.  At  the 
trial.  Profs.  DragendorfP  and  Uslar,  being  called  by  the  defence, 
declared  in  the  most  positive  manner  that  strychnine  should  always 
be  recovered,  even  if  the  body  had  been  buried  four  months.  Owing 
to  these  declarations,  the  accused  was  acquitted.  {Ann.  d'Hyg., 
March,  1880,  278.) 

To  determine  how  far  these  allegations  of  Profs.  Dragendorlf 
and  Uslar  were  true.  Profs.  Buchner,  Gorup-Besanez,  and  Wis- 
licenus,  as  chemists,  and  Prof.  Ranke,  as  physiologist,  made  a  series 
of  experiments  upon  seventeen  dogs,  each  killed  by  0.1  gramme 
(IJ  grain)  of  strychnine  nitrate  (a  fatal  dose  for  man).  The  buried 
bodies  of  the  animals  were  variously  exhumed  and  examined  at  the 
end  of  one  hundred,  one  hundred  and  thirty,  two  hundred,  and 
three  hundred  and  thirty  days.  As  the  result,  in  all  cases  the 
chemical  tests  failed  to  reveal  the  presence  of  strychnine.  Neverthe- 
less, in  every  instance,  even  in  the  dog  exhumed  at  the  end  of  three 
hundred  and  thirty  days,  the  presence  of  the  poison  could  be  inferred 
from  the  bitter  taste  of  the  obtained  product.  Moreover,  the  ex- 
tracts obtained  by  each  of  the  chemists,  and  in  which  strychnine 
could  not  be  discovered  chemically,  when  dissolved  and  injected  into 
frogs,  caused  within  a  few  minutes  violent  tetanic  convulsions.  These 
convulsions  were  the  more  rapid  and  intense  in  proportion  to  the 
shortness  of  time  the  dogs  were  buried,  being,  however,  still  very 
evident  in  the  extract  from  the  dog  buried  three  hundred  and  thirty 
days.     {Ann.  d'Hyg.,  April,  1881,  385.) 


DETECTIO?^    AFTER    LONG    PERIODS.  599 

III  :i  caso  wc  exjiniined  in  1875,  in  which  a  woman  was  suddenly 
seized  with  violent  tetanic  convulsions,  and  died  within  two  hours 
under  most  niari^ed  symptoms  of  stryehninc  poisoning,  the  stomach 
with  its  contents  and  a  portion  of  the  liver,  examined  seven  months 
after  death,  furnished  extracts  having  an  intensely  hitter  taste;  but 
in  no  instance  did  the  chemical  tests  for  strychnine  yield  satisfactory 
evidence  of  the  presence  of  the  poison.  The  husband  of  the  de- 
ceased was  tried  for  the  poisoning,  and  found  guilty  of  murder  in 
the  second  degree.  {State  of  Ohio  v.  /.  Dresbach,  1881.)  In  another 
case,  we  readily  found  strychnine  in  the  stomach  of  a  child  that  had 
died  from  the  effects  of  the  alkaloid,  and  in  which  the  organ  was 
removed  from  the  exhumed  body  two  weeks  after  death,  and  pre- 
served in  alcohol  five  weeks  longer. 

Although  in  experiments  upon  animals  and  in  preserved  organic 
mixtures,  strychnine  has  been  repeatedly  found  after  very  long 
periods,  yet  the  longest  period  in  which  the  analysis  furnished 
positive  evidence  of  its  presence  in  the  exhumed  human  body  is 
forty-three  days  after  death.  [Ann.  d^Hyg.,  April,  1881,  359.)  In 
a  body  in  which  the  examination  was  made  nearly  four  months,  and 
in  another  something  over  a  year,  after  burial,  no  trace  of  the  poison 
was  found. 

In  a  case  reported  by  Dr.  A.  A.  Hayes,  he  recovered  over  half  a 
grain  of  crystallized  strychnine  from  the  fourth  part  of  the  contents 
of  the  stomach  two  weeks  after  death,  the  post-mortem  having  been 
made  ten  days  after  death.  In  this  instance  as  much  as  twenty 
grains  of  strychnine  may  have  been  taken.  (Boston  Med.  and  Surg. 
Jour.,  March,  1861,  133.)  Strychnine  has  also  been  recovered  from 
the  human  subject  after  three  weeks,  one  month,  and  at  the  end  of 
five  weeks.     [Ann.  d'Hyg.,  April,  1881,  354.) 

At  the  trial  of  Mary  Freet,  charged  with  the  murder  of  her 
husband  by  strychnine,  it  was  alleged  that  a  few  weeks  prior  to  the 
administration  of  the  fatal  dose  the  defendant  prepared  a  bowl  of 
mush  and  milk  for  the  deceased,  and  that  he  complained  of  its 
having  a  bitter  taste,  and  threw  the  contents  of  the  bowl  into  the 
yard  ;  and  that  afterward  a  cat  having  eaten  the  mush  very  suddenly 
died.  A  chemical  examination  of  the  contents  of  the  stomach  of 
the  animal  two  months  after  death,  the  body  having  part  of  the  time 
been  exposed  in  a  common  alley,  clearly  revealed  the  presence  of 
strychnine. 


600  BRUCINE. 

Quantitative  Analysis. — The  quantity  of  strychnine  present 
in  a  pure  aqueous  solution  of  any  of  its  salts  may  be  estimated 
with  sufficient  accuracy  for  ordinaiy  purposes  by  treating  the  some- 
what concentrated  solution  with  slight  excess  of  a  caustic  alkali,  and 
allowing  the  mixture  to  stand  in  a  cool  place  for  from  twelve  to 
twenty-four  hours,  when  the  deposit  will  have  assumed  the  crystal- 
line form.  The  precipitate  is  then  collected  on  a  small  equipoised 
filter,  washed  with  a  small  quantity  of  cold  water,  dried  on  a  water- 
bath,  and  weighed.  Since  strychnine  is  not  wholly  insoluble  in 
water,  even  in  the  presence  of  a  free  alkali,  a  minute  portion  of  the 
alkaloid  will  remain  in  the  alkaline  liquid.  The  quantity,  however, 
that  may  thus  escape  precipitation  will  rarely  exceed  the  l-10,000th 
part  by  weight  of  the  fluid  present.  If  on  extracting  the  alkaloid 
from  its  aqueous  solution  by  means  of  chloroform  or  ether,  it  is  left, 
on  evaporation  of  the  liquid,  in  its  pure  state,  it  may,  of  course,  be 
at  once  weighed.  One  hundred  parts  by  weight  of  the  alkaloid 
correspond  to  about  133  parts  of  the  pure  crystallized  sulphate,  118 
parts  of  the  acetate,  or  about  120  parts  of  crystalliced  hydrochloride 
of  strychnine. 

III.  Brucine. 

History. — Brucine,  or  brucia,  occurs  in  most  if  not  all  of  the 
Strychnos  plants  in  which  strychnine  is  found.  It  was  first  dis- 
covered, in  1819,  by  Pelletier  and  Caventou,  in  what  was  formerly 
known  as  false  Angustura  bark,  but  which  has  since  been  shown  to 
be  the  bark  of  the  nux  vomica  tree.  It  occurs  both  in  the  bark  and 
seed  of  this  tree  ;  in  the  bark — which  contains  less  strychnine  and 
more  brucine  than  the  seed — it  is  said  to  be  in  combination  with 
gallic  acid,  while  in  the  seed  it  is  believed  to  be  combined  with 
strychnic  acid.  The  proportion  of  brucine  in  nux  vomica  is  said 
to  vary  from  0.12  to  1.10  per  cent.  The  composition  of  the  an- 
hydrous alkaloid,  according  to  Regnault,  is  CagHggjSTaO^. 

Preparation. — Brucine  may  be  obtained  from  the  bark  of  nux 
vomica  in  a  manner  similar  to  that  by  which  strychnine  is  obtained 
from  the  seed,  except  that  the  alcoholic  extract  obtained  from  the 
precipitate  produced  by  lime  is  treated  with  oxalic  acid,  and  subse- 
quently with  a  mixture  of  alcohol  and  ether,  which  dissolves  the 
coloring  matter,  while  the  oxalate  of  brucine  remains  undissolved. 
This  salt  is  then  decomposed  by  magnesia,  and  the  liberated  brucine 


GENERAT.  CHEMICAL  NATURE. 


()01 


dissolved   in  alcohol,  wliich  on  si)on(aiR>()iis  evaporation  leaves  the 
alkaloid  in  its  crystalline  state. 

rhysiolof/icnl  7^ec/.s'.— The  effects  oi"  hnicinc  on  tin;  animal 
economy  arc  precisely  the  same  in  kind  as  those  of  strychnine ;  but 
it  is  less  energetic  in  its  action  than  the  latter  alkaloid,  having 
only  about  one-twelfth  the  power  of  that  substance.  Dr.  Christison 
cites  two  instances  of  poisoning  by  this  substance;  and  Prof.  Casper 
relates  three  cases  in  which  death  resulted  from  the  taking  of  a 
mixture  of  arsenic  and  brucine.  {Forensic  Medicine,  ii.  102.)  In 
a  case  related  by  Dr.  T.  S.  Sozinskey  {Med  and  Surg.  Rep.,  Aug. 
1882,  194),  two  grains  of  brucine  taken  by  a  man  produced  most 
alarm'ing  symptoms,  essentially  the  same  as  those  produced  by  strych- 
nine :  under  active  treatment  the  patient  entirely  recovered.  The 
ordinary  medicinal  dose  of  brucine  is  from  half  a  grain  to  one  grain, 
repeated  two  or  three  times  a  day. 

General  Chemical  Natuee.— Brucine  is  a  white,  odorless 
solid,  having  an  intensely  bitter  taste,  very  similar  to  that  of  strych- 
nine. In  its  pure  state  it  is  readily  crystallizable,  forming  beautiful 
groups  of  very  delicate,  transparent  needles ;  when  the  crystals  are 
only  slowly  produced,  they  usually  appear  in  the  form  of  bold, 
colorless,  four-sided  prisms :  the  crystals  contain  four  molecules,  or 
about  15.45  per  cent,  of  their  weight,  of  water  of  crystallization, 
their  composition  being  CssH^eNA-^H.O.  When  moderately  heated, 
the  crystals  fuse  and  become  anhydrous ;  and  at  a  higher  temperature 
the  residue  takes  fire  and  burns  with  a  dense  smoky  flame.  Brucine 
may  be  sublimed  unchanged.  According  to  Prof.  Guy,  the  alka- 
loid fuses  at  115.5°  C.  (240°  F.)  and  sublimes  at  204.4°  C.  (400°  F.), 
the  sublimate  being  generally  amorphous.  {Forensic  Medicine,  1881, 
576.)  Brucine  is  unacted  upon  by  the  fixed  caustic  alkalies,  but  it  is 
readilv  decomposed  by  concentrated  nitric  acid. 

The  salts  of  brucine  are  colorless,  except  when  they  contain  a 
colored  acid,  and  are  for  the  most  part  easily  crystallizable.  They 
have  the  bitter  taste  of  the  pure  alkaloid,  and  are  readily  decora- 
posed  by  the  caustic  alkalies,  with  the  elimination  of  the  brucine. 
In  regard  to  its  basic  properties,  brucine  is  somewhat  inferior  to 
strychnine,  it  being  displaced  from  its  saline  combinations  by  that 

alkaloid. 

Solubility.— When  excess  of  pure  powdered  brucine  is  frequently 
agitated  with  pure  water  at  the  ordinary  temperature  for  twenty-four 


602  BEUCINE. 

hours,  one  part  of  the  crystallized  alkaloid  dissolves  in  900  parts  of 
the  liquid :  this  corresponds  to  one  part  of  the  anhydrous  alkaloid 
in  about  1050  parts  of  the  menstruum.  It  is  much  more  soluble  in 
hot  water,  from  which,  however,  the  greater  part  of  the  excess  sepa- 
rates as  the  solution  cools.  Its  solubility  in  this  liquid  is  somewhat 
increased  by  the  presence  of  foreign  organic  matter. 

Absolute  ether,  when  frequently  agitated  for  several  hours  at  the 
ordinary  temperature  with  excess  of  the  powdered  alkaloid,  dissolves 
one  part  of  the  anhydrous  base  in  440  parts  of  the  liquid.  Chloro- 
form readily  dissolves  the  alkaloid  in  nearly  every  proportion.  It 
is  thus  obvious  that  this  liquid  is  better  adapted  than  ether  for 
the  separation  of  the  alkaloid  from  alkaline  aqueous  mixtures.  The 
alkaloid  is  also  readily  soluble  in  nearly  every  proportion  in  absolute 
alcohol.  But  it  is  insoluble  in  the  fixed  caustic  alkalies,  and  only 
sparingly  soluble  in  large  excess  of  ammonia.  Most  of  the  salts  of 
brucine  are  freely  soluble  in  water  and  in  alcohol. 

Special  Chemical  Properties. — Concentrated  sulphuric  acid 
dissolves  brucine  and  its  salts  with  the  production  of  a  faint  rose-red 
color.  If  the  acid  contains  nitric  acid — as  is  frequently  the  case — 
the  alkaloid  dissolves  to  a  deep  red  solution.  If  a  small  crystal  of 
potassium  dichromate  be  stirred  in  the  sulphuric  acid  solution,  the 
liquid  acquires  an  orange  or  brownish-orange  color,  which  slowly 
changes  to  a  greenish  hue,  due  to  the  separation  of  chromium  oxide. 
This  reaction  at  once  distinguishes  brucine  from  strychnine.  Con- 
centrated nitric  acid  dissolves  the  alkaloid,  as  well  as  its  salts,  to  a 
deep  red  solution,  the  color  of  which  slowly  fades  to  yellow.  The 
statement  of  Sonnenschein,  that  under  the  action  of  nitric  acid  bru- 
cine is  converted  into  strychnine,  has  not  been  confirmed  by  more 
recent  observers.  Brucine  is  readily  soluble  in  concentrated  hydro- 
chloric acid  without  change  of  color. 

In  the  following  examination  of  the  reactions  of  solutions  of 
brucine,  the  pure  crystallized  alkaloid  was  dissolved,  by  the  aid  of 
just  sufficient  acetic  or  sulphuric  acid,  in  pure  water.  The  fractions 
employed  indicate  the  fractional  part  of  a  grain  of  the  crystallized 
alkaloid  in  solution  in  one  grain  of  water;  and  the  results,  unless 
otherwise  indicated,  refer  to  the  behavior  of  one  grain  of  the  solution. 
One  grain  of  pure  crystallized  brucine  corresponds  to  0.845  of  a  grain 
of  the  anhydrous  alkaloid. 


nitrk;  acid  and  stannous  chloride  test.  603 

1 .   The  Caustic  Alkalies. 

The  fixed  caustic  alkalies  and  ammonia  produce  in  concentrated 
solutions  of  salts  of  hrucine  a  white,  amorj)lious  |)r(!cipitate  of  the  pure 
anhydrous  alkaloid,  which  after  a  little  time,  by  the  assimilation  of 
water,  assumes  the  crystalline  form.  The  precipitate  is  readily  soluble 
in  free  acids,  even  in  acetic  acid;  but  it  is  insoluble  in  large  excess 
of  cither  potassium  or  sodium  hydrate.  In  its  amorphous  state  the 
precipitate  is  rather  freely  soluble  in  large  excess  of  ammonia;  but 
wlien  it  has  assumed  the  crystalline  form  it  is  only  very  sparingly 
soluble  in  that  liquid. 

1.  ^_^  grain  of  brucine,  in  one  grain  of  water,  yields  with  either  of 

the  fixed  alkalies  an  immediate  amorphous  precipitate,  which  in 
a  very  little  time  gives  rise  to  very  beautiful  groups  of  exceed- 
ingly delicate  crystalline  needles,  Plate  XI.,  fig.  5 ;  and  soon  the 
mixture  becomes  converted  into  a  nearly  solid  mass  of  crystals. 
Ammonia  produces  a  similar  precipitate,  but  it  does  not  usually 
appear  until  after  some  little  time ;  it  then  separates  in  the  crys- 
talline form.  If  large  excess  of  ammonia  be  added,  the  precipi- 
tate may  fail  to  appear,  even  after  several  hours. 

2.  -g-^  grain  yields  with  a  fixed  alkali  an  immediate' cloudiness,  and 

soon  a  very  good  crystalline  precipitate.     The  formation  of  the 
precipitate  is  much  facilitated  by  stirring  the  mixture.     Very- 
similar  results  may  be  obtained  by  ammonia,  provided  it  be 
added  in  very  minute  quantity. 
Solutions  of  salts  of  brucine  but  little  more  dilute  than  the  last- 
mentioned  fail  to  yield  a  precipitate  hy  either  of  the  caustic  alkalies. 
The  alkali  carbonates  behave  with  solutions  of  salts  of  brucine 
in  much  the  same  manner  as  the  free  alkalies.     The  true  nature  of 
the  precipitate  produced  by  the  caustic  alkalies  may  be  confirmed  by 
either  of  the  two  next-mentioned  tests, 

2.  Nitric  Acid  and  Stannous  Chloride. 

If  a  few  crystals  of  brucine  or  of  any  of  its  colorless  salts,  in  the 
dry  state,  be  treated  with  a  drop  of  concentrated  nitric  acid,  they  im- 
mediately assume  a  deep  blood-red  color,  and  quickly  dissolve  to  a 
solution  of  the  same  hue ;  on  heating  this  solution  its  color  is  changed 
to  orange-yellow  or  yellow.  If,  when  the  solution  has  cooled,  a  drop 
of  a  solution  of  stannous  chloride  be  added,  the  mixture  immediately 


604  BRUCINE. 

acquires  a  beautiful  'purple  color,  which  is  discharged  by  large  excess 
of  either  nitric  acid  or  of  the  tin  compound,  as  also  by  sulphurous 
oxide  gas.  The  red  color  of  nitric  acid  solutions  of  brucine  contain- 
ing a  quite  notable  quantity  of  the  alkaloid  is  changed  to  a  faint 
purple  on  the  addition  of  the  tin  solution  alone,  without  the  appli- 
cation of  heat:  but  the  intensity  of  the  color,  as  thus  obtained,  is 
much  inferior  to  that  obtained  from  the  brucine  solution  after  it  has 
been  heated;  and  if  only  a  minute  quantity  of  the  alkaloid  be 
present,  without  the  application  of  heat,  the  purple  color  entirely 
fails  to  appear. 

The  following  quantities  of  brucine  were  obtained  by  evaporating 
one  grain  of  the  corresponding  solution  of  the  acetate  to  dryness  on  a 
water- bath. 

1.  YWQ  gi'&i^i  of  brucine  dissolves  in  a  drop  of  nitric  acid  to  a  deep 

red  solution,  which,  when  heated  and  allowed  to  cool,  and  then 
treated  with  the  tin  compound,  acquires  an  intense  purple  color. 

2.  y-^oo"  grain  :  the  drop  of  acid  acquires  a  very  satisfactory  red  color, 

which  upon  the  addition  of  the  tin  salt,  after  the  solution  has 
been  heated,  is  changed  to  a  beautiful  lilac. 

3.  xFiWo"  gi^'ai"  :  on  the  addition  of  a  very  small  drop  of  the  acid 

the  deposit  assumes  a  very  decided  red  color,  and  dissolves  to  a 
faint  red  solution ;  the  tin  salt  produces  a  quite  distinct  lilac 
coloration.  To  obtain  the  latter  color  the  acid  and  tin  compound 
must  be  well  apportioned,  otherwise  the  reaction  may  entirely 
fail  to  manifest  itself.    This  is  about  the  limit  of  the  tin  reaction. 

4.  5o-,oT¥  grain,  when  moistened  with  a  minute  trace  of  the  acid, 

assumes  a  quite  perceptible  red  color;  if  this  njixture  be  evapo- 
rated to  dryness,  on  a  water-bath,  it  leaves  a  very  satisfactory 
red  deposit. 

5.  YF^iroir  gi'aiu,  when  treated  as  under  4,  leaves  a  quite  distinct  red 

residue. 
These  reactions  of  nitric  acid  and  stannous  chloride,  when  taken 
in  connection,  are  quite  characteristic  of  brucine ;  and  at  the  same 
time,  as  we  have  just  seen,  are  exceedingly  delicate.  In  these 
respects  this  test  bears  much  the  same  relation  to  brucine  that  the 
color  test  does  to  strychnine.  Xitric  acid  also  produces  a  red  color 
with  morphine  and  with  several  other  substances  besides  brucine  ;  but 
the  subsequent  addition  of  stannous  chloride  fails  to  produce,  with 
any  of  these  fallacious  solutions,  a  purple  coloration.     The  red  color 


POTASSIUM   SUI-IMIOCVANIDK   TKST.  005 

of  (lu-  acid  solution  of  moritliine  is  hut  little  afreotcd  l)y  tin;  tin  coni- 
poiuul,  at  most  beini^  changed  to  ycillow;  when  the  acid  sohuioii  lias 
been  heated  and  allowed  to  cool,  the  tin  salt  produces  no  visible 
change. 

3.  Sulphwic  Acid  and  Potassium  Nitrate. 

Briieine  and  its  salts,  as  already  pointed  out,  dissolve  in  concen- 
trated sulphuric  acid  with  the  production  of  a  rose-red  color.  If  a 
crystal  of  potassium  nitrate  be  stirred  in  the  solution,  the  mixture 
acquires  a  deep  oi||nge-red  color,  due  to  the  action  of  the  nitric  acid 
of  the  nitre.  This  test,  therefore,  is  very  similar  in  its  action  to  the 
one  just  considered. 

1.  ^^  grain  of  brucine,  when  treated  with  a  small  drop  of  concen- 

trated sulphuric  acid,  dissolves  to  a  solution  having  a  faint  rose 
color,  which  on  the  addition  of  a  small  crystal  of  nitre  is  changed 
to  deep  orange-red. 

2.  .^-^  grain  :  on  the  addition  of  the  acid  the  deposit  assumes  a 

quite  perceptible  rose- red  color,  and  dissolves  to  a  colorless  solu- 
tion, which  on  the  addition  of  the  nitre  acquires  a  beautiful 
orange  color. 

3.  j-^-^  grain  :  the  acid  dissolves  the  deposit  with  little  or  no  change 

of  color;  but  the  solution,  when  treated  with  the  potassium  salt, 
acquires  an  orange  color,  which  soon  changes  to  yellow. 

4.  -^^-^-Q-jj-  grain  :  when  the  acid  solution  is  treated  with  the  nitre  it 

yields  only  a  faintly  yellow  coloration.     But  if  a  small  crystal 
of  nitre  be  moistened  with  the  acid  and  then  stirred  over  the 
dry  brucine  deposit,  the  crystal  acquires  a  distinct  orange  color. 
The  production  of  these  colors  is  quite  peculiar  to  brucine.     Sul- 
phuric acid  solutions  of   narcotine,   opianyl,  and   morphine,   when 
treated  with  potassium  nitrate,  yield  colors  somewhat  similar  to  that 
produced  from  brucine;  but  neither  of  these  substances  dissolves  in 
the  acid  with  the  production  of  a  rose-red  color. 

4.  Potassium  Sulphoeyanide. 

This  reagent  throws  down  from  quite  concentrated  solutions  of 
salts  of  brucine  a  white  precipitate  of  brucine  sulphoeyanide,  which 
is  insoluble  in  acetic  acid.  As  produced  from  very  concentrated  so- 
lutions, the  precipitate  is  in  the  amorphous  form,  but  it  soon  becomes 
more  or  less  crvstalline.     From  somewhat  more  dilute  solutions  the 


606  BRUCINE. 

precipitate  does  not  appear  until  after  some  time,  and  it  then  sepa- 
rates in  the  form  of  small  granules.  The  formation  of  the  precipi- 
tate from  solutions  of  this  kind  is  much  facilitated  by  stirring  the 
mixture  with  a  glass  rod. 

One  grain  of  a  1-lOOth  solution  of  the  alkaloid  yields  no  im- 
mediate precipitate,  but  in  a  few  moments  comparatively  large  groups 
of  minute  granules  appear,  and  after  a  few  minutes  there  is  a  quite 
good  deposit  of  these  groups,  with  occasionally  small  transparent 
crystalline  plates,  Plate  XI.,  fig.  6.  A  similar  quantity  of  a  l-500th 
solution  fails  to  yield  a  precipitate,  even  when  theguixture  is  allowed 
to  stand  for  some  hours. 

5.  Potassium  Dichromate. 

Potassium  dichromate  throws  down  from  solutions  of  salts  of 
brucine,  even  when  highly  diluted,  a  yellow  precipitate  of  bruciue 
chromate,  which  is  insoluble  in  acetic  acid.  The  precipitate  is 
readily  soluble,  with  the  production  of  a  deep  red  color,  in  con- 
centrated nitric  acid,  and  in  sulphuric  acid,  with  the  production  of 
a  reddish-brown  color. 

1.  yig-  grain  of  brucine,  in  one  grain  of  water,  yields  a  quite  copious 

amorphous  precipitate,  which  in  a  few  moments  becomes  con- 
verted into  crystalline  group?  of  the  forms  illustrated  in  Plate 
XIL,  fig.  1.  ' 

2.  YWoT  g^-'^^^  ■  i^    ^^^^   mixture    be   stirred,   it   immediately  yields 

streaks  of  granules  and  small  crystals  along  the  path  of  the 
rod,  and  in  a  little  time  there  is  a  quite  copious  crystalline 
deposit. 

3.  gQ^QQ  grain  yields  after  a  little  time,  especially  if  the  mixture  has 

been  stirred,  a  quite  satisfactory  crystalline  precipitate. 

4.  3-0,^-0-0  grain  :  after  several  minutes  a  quite  distinct  precipitate, 

and  after  about  half   an   hour  a  very  satisfactory   deposit   of 
crystalline  needles. 
The  crystalline  form  of  the  precipitate,  as  produced  from  some- 
what strong  solutions  of  the  alkaloid,  together  with  the  subsequent 
reaction  of  nitric  acid,  serves  to  distinguish  the  chromate  of  brucine 
from  all  other  precipitates  produced  by  this  reagent. 

Potassium  monochromate  produces  in  solutions  of  the  alkaloid 
results  very  similar  to  those  occasioned  by  the  dichromate,  only  that 
the  reaction  is  not  quite  so  delicate. 


AURIC   CHLORIDE   TEST.  007 


6.  Platinic  Chloride. 


Solutions  of  salts  of  hnicine  yield  with  platinic  cliloriile  a  yel- 
low j)rec'i|)itate  of  the  double  chloride  of  ])latinuni  and  briiciiie, 
2C23H2,5N204,HC1 ;  PtCl.,,  which  is  uiichaiigcd  by  acetic  acid,  l)Ut 
readily  decomposed  by  tiie  caustic  alkalies. 

1.  y\-^  tiTain  of  brucine  yields  a  very  copious  deposit,  which  almost 

immediately  becomes  a  mass  of  irregular  crystalline  needles. 
The  precipitate  is  slowly  soluble  in  nitric  acid,  yielding  an 
orange- red  solution. 

2.  -Y-iijT)   grain :   an  immediate  light  yellow,  crystalline  precipitate, 

which  in  a  little  time  becomes  converted  into  irregular  needles, 
Plate  XII.,  fig.  2. 

3.  -suVo   grain  :  very  soon  crystals  appear,  and  after  a  little  time 

there  is  a  quite  good  crystalline  deposit. 

4.  YTj-.VoTT  gi'ain :  if  the  mixture  be  stirred,  it  immediately  yields 

crystalline  streaks,  and  very  soon  a  quite  fair  deposit. 

5.  yg-.VFo   grain:    after  a   few   minutes,   if   the  mixture  has   been 

stirred,  crystalline  needles  appear,  and  after  a  little  time  there 

is  a  quite  satisfactory  deposit. 
This  reagent  also  produces  yellow  crystalline  precipitates  with 
various  other  substances,   but  the  form  of  the  brucine  deposit  is 
somewhat  peculiar. 

7.  Auric  Chloride. 

This  reagent  produces  in  solutions  of  salts  of  brucine  a  vellow, 
amorphous  precipitate  which  has  the  composition  C23H2j;N204,IICl, 
AuClg,  and  which  in  a  little  time  acquires  a  flesh  color.  The  pre- 
cipitate is  but  sparingly  soluble  in  acetic  acid ;  the  caustic  alkalies 
cause  it  quickly  to  assume  a  dark  color. 

1.  370^  grain  of  brucine,  in  one  grain  of  water,  yields  a  very  copious 

deposit. 

2.  y^Vo    gi'iiiu    yields   a   greenish-yellow    precipitate,    which    soon 

becomes  yellow ;  the  deposit  is  readily  soluble  to  a  clear  solu- 
tion in  potassium  hydrate. 

3.  Yo.Voir  gi'iiin  =  a  quite  good,  yellowish  deposit. 

4.  i2^,Vuir  griiin  yields  in  a  very  little  time  a  distinct  turbidity,  and 

after  a  few  minutes  a  quite  satisfactory  precipitate. 

5.  ^-o.-gird  grain  :  after*  some  minutes  a  quite  distinct  deposit. 


608  BRUCINE. 

All  these  precipitates  remain  amorphous.  The  reaction  of  this 
reagent  is  common  to  a  large  class  of  substances. 

8.  Picrio  Acid. 

An  alcoholic  solution  of  picric  acid  throws  down  from  aqueous 
solutions  of  salts  of  brucine  a  yellow  precipitate  of  brucine  picrate, 
which  is  but  sparingly  soluble  in  large  excess  of  acetic  acid. 

1.  Y^  grain  of  brucine  yields  a  very  copious  precipitate,  which  after 

a  time  becomes,  in  part  at  least,  crystalline.  The  formation  of 
these  crystals  is  readily  prevented  by  the  presence  of  foreign 
organic  matter. 

2.  Y^ro  g'^&i'^i  yields  a  very  good  precipitate,  which  after  a  time  is 

converted  into  groups  of  aggregated  granules,  similar  to  those 
produced  by  potassium  sulphocyanide  (Plate  XL,  fig.  6). 

3.  3-o-,Vro  g^^^ii^  yields  after  several  minutes,  especially  if  the  mix- 

ture has  been  stirred,  a  quite  distinct  precipitate. 
The  reaction   of   this  reagent  is  valuable  only  in  so  far  as  it 
confirms  tne  reactions  of  the  other  tests  for  brucine. 

9.  Potassium  Ferricyanide. 

Concentrated  neutral  solutions  of  salts  of  brucine,  when  treated 
with  this  reagent,  yield  a  light  yellow,  crystalline  precipitate,  which 
is  readily  soluble  in  the  mineral  acids.  The  formation  of  the  pre- 
cipitate is  readily  prevented  by  the  presence  of  a  free  acid,  even 
of  acetic  acid,  but  after  the  crystals  have  formed  they  are  only  very 
sparingly  soluble  in  large  excess  of  acetic  acid. 

1.  yi-^  grain  of  brucine  yields  an  immediate  precipitate,  and  in  a 

few  moments  there  is  a  very  copious  deposit  of  crystals,  grouped 
in  various  and  most  beautiful  forms,  Plate  XII.,  fig.  3.  These 
crystalline  groups  are,  perhaps,  the  most  brilliant  polariscope 
objects  yet  known.  The  production  of  these  crystals  is  quite 
characteristic  of  brucine. 

2.  -g-l-Q-  grain  :  after  stirring  the  mixture  it  yields  in  a  very  little 

time  a  copious  granular  deposit. 

3.  YrQ-g-  grain :  after  some  time  a  slight  turbidity. 

Potassium  ferrocyanide  produces  no  precipitate  with  a  1— 100th 
solution  of  brucine,  even  if  the  mixture  be  allowed  to  stand  for  some 
time. 


SPECIAL   CHEMICAL   PROPERTIES.  609 

10.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  produces  in  normal 
solutions  of  salts  of  brucinc,  even  when  very  liigiily  diluted,  an 
orange-brown,  amorphous  precipitate,  which  is  insoluble  in  acetic 
acid. 

1.  yJ-jj-  grain   of    brucine    yields  a  very  copious  deposit,  which   is 

decomposed   by   large  excess  of  ])otassium   hydrate,  with   the 
production  of  a  dirty- white  precipitate. 

2.  Yjyjj-  grain  :  much  the  same  results  as  1. 

3.  X(7,-o-irir  gi'^^'i  yields  a  quite  good,  brownish  precipitate,  which  is 

soluble  to  a  clear  solution  in  a  caustic  alkali. 

4.  -s-g-.^ouir  gi'^'w  yields  a  yellowish  deposit. 

5.  Ti5-ij,oirir  grain  :  a  very  distinct,  dirty-yellowish  turbidity. 

6.  -sij-o^^y-o  grain  yields  a  perceptible  cloudiness. 

It  need  hardly  be  remarked  that  this  reagent  produces  similar 
precipitates  in  solutions  of  most  of  the  alkaloids  and  of  various  other 
organic  substances. 

11.  Bromine  in  Bromohydrlc  Acid. 

A  strong  aqueous  solution  of  bromohydric  acid  saturated  with 
bromine  produces  in  solutions  of  salts  of  brucine,  when  not  too 
dilute,  a  deep  brown,  amorphous  precipitate,  which  after  a  time  dis- 
solves, but  is  reproduced  upon  further  addition  of  the  reagent.  The 
precipitate  is  soluble  in  acids,  even  acetic  acid,  and  in  potassium 
hydrate. 

1.  Y^  grain  of  brucine  yields  a  very  copious,  deep  brown  deposit, 

which  soon  acquires  a  yellow  color,  then  a  bright  yellow,  and 
after  some  minutes  dissolves. 

2.  ythmj-  grain  :  much  the  same  results  as  1. 

3.  YTj.^inr  grain  yields  a  yellowish  precipitate,  which  after  a  time 

disappears,  and  is  not  reproduced  upon  further  addition  of  the 
reagent. 

4.  ■2^,Vgt  grain  yields  a   greenish-yellow  deposit,  which  soon  dis- 

solves. 
The  brown  color  of  the  brucine  deposit  distinguishes  it  from  the 
precipitates  produced  by  this  reagent  with  other  alkaloids. 

Other  Bcadions. — S.  Cotton  has  shown  that  when  a  icarmed  nitric 

39 


610  BEUCINE. 

acid  solution  of  brucine  is  treated  with  a  concentrated  solution  of 
sodium  hydrosulphide,  the  mixture  assumes  a  beautiful  violet  color, 
which  is  changed  to  g^'een  by  large  excess  of  the  reagent.  This  color 
is  not  atfected  by  the  alkalies,  but  diluted  acids  change  it  to  rose- 
red,  sulphuretted  hydrogen  being  evolved.  [Jour.  Pharm.  et  Chim., 
July,  1869,  18.)  The  reagent  may  be  prepared  by  saturating  a 
strong  solution  of  sodium  hydrate  (1  :  8)  with  sulphuretted  hydrogen 
gas. 

To  apply  this  test,  a  few  drops  of  the  brucine  solution,  placed 
in  a  small  test-tube,  are  treated  with  a  few  drops  of  nitric  acid,  the 
mixture  warmed  to  40°  or  50°  C.  (about  115°  F.),  and  then  a  drop 
or  two  of  the  reagent  added.  In  this  manner  a  1-1 000th  solution 
of  brucine  will  yield  a  deep  violet  coloration,  which  under  excess  of 
the  reagent  is  changed  to  green.  A  l-10,000th  solution  yields  a 
very  good  violet  or  purple  coloration,  passing  to  deep  green  under 
excess  of  the  reagent.  Even  a  l-1 00,000th  solution  will  yield  a 
distinct  purple,  followed  by  a  perceptible  green  coloration.  Strych- 
nine yields  no  color  under  this  test,  and  morphine  fails  to  yield  a 
similar  coloration. 

Mereurous  nitrate,  free  from  excess  of  nitric  acid,  occasions  no 
coloration  with  solutions  of  salts  of  brucine  in  the  cold ;  but  if  the 
mixture  be  heated  on  a  water-bath,  a  beautiful  carmine  color  is  grad- 
ually developed,  which  is  permanent  on  evaporating  the  liquid  to 
dryness.  This  coloration  is  very  intense  in  a  few  drops  of  a  1-1 00th 
solution  of  brucine;  and  the  residue  from  a  similar  quantity  of  a 
l-10,000th  solution  has  a  well-marked  pinkish  hue.  According  to 
F.  A.  Fhickiger,  who  first  observed  this  reaction,  strychnine,  the 
alkaloids  of  opium  and  cinchona,  veratrine,  caffeine,  and  piperine, 
})roduce  no  color  under  these  conditions;  but  albumin  and  phenol 
yield  similar  colorations. 

Prof.  DragendorfP  has  lately  shown  (1878)  that  if  brucine  be 
dissolved  in  diluted  sulphuric  acid  (1  :  10),  and  a  minute  quantity 
of  a  very  dilute  aqueous  solution  of  potassium  dichromate  be  then 
added,  the  mixture  acquires  a  beautiful  red  color,  changing  to  red- 
dish-orange, then  to  brownish- orange,  the  reaction  being  one  of 
oxidation.  Under  this  reaction  a  coloration  will  manifest  itself,  as 
claimed  by  Dragendorfi',  in  a  1-1 0,000th  solution  of  the  alkaloid. 

According  to  Watson  Smith,  if  solid  brucine  be  let  fall  upon 
antimony  trichloride  heated  to  fusion,  a  beautiful  red  or  purple-red 


SEPARATION    FROM    ORGANIC    MIXTURES.  Oil 

color  is  developed,  oven  when  only  the  minutest  trace  of  the  alkaloid 
is  employed.  {C/ievi.  Neios,Ju\y,  1879.)  Mr.  Smith  states  (hat  this 
reaction  is  peculiar  to  hrucine. 

Corro.sii'c  tiiib/iinatc  thi'ows  down  from  a  1-lOOth  solution  of  salts 
of  hrucine  a  quite  j2;<iod,  white,  amorphous  precipitate,  which  soon 
becomes  i2;ianular ;  with  solutions  hut  little  more  dilute  than  this 
the  rca<:;ent  fails  to  i)roduce  a  precipitate.  PotaHHiani  iodide  produces 
in  a  1-lOOth  solution  of  the  alkaloid  no  immediate  precipitate,  but 
after  a  time  there  is  a  quite  good  deposit  of  rough  needles  and  crys- 
talline plates.  Tannic  acid  throws  down  from  even  highly  diluted 
solutions  of  the  alkaloid  a  dirty-white,  amorphous  precipitate,  which 
is  soluble  in  acetic  acid. 

Chlorine  gas  passed  into  concentrated  solutions  of  salts  of  brucine 
produces  at  first  a  yellow,  then  a  red  color,  which  is  discharged  by 
excess  of  the  gas.  Upon  the  subsequent  addition  of  ammonia,  the 
liquid  acquires  a  light  brown  color.  These  reactions  manifest  them- 
selves only  in  very  strong  solutions  of  salts  of  the  alkaloid. 

Administered  to  frogs,  brucine  produces  violent  tetanic  convul- 
sions, similar  to  those  occasioned  by  strychnine,  but  their  production 
requires  relatively  a  much  larger  quantity  of  the  former  than  of  the 
latter  alkaloid. 

Since  the  symptoms  produced  by  strychnine  and  brucine  are  so 
very  similar  in  their  nature,  the  examiner  should  bear  this  in  mind 
in  a  case  of  suspected  poisoning,  especially  when  the  tests  for  the 
former  alkaloid  have  failed  to  show  its  presence. 

Separation  from  Organic  Mixtures. 

Brucine  may  be  separated  from  organic  mixtures  in  the  same 
manner  as  heretofore  directed  for  the  recovery  of  strychnine.  "When 
the  analysis  furnishes  only  a  small  residue  for  the  application  of  the 
chemical  tests,  a  portion  of  it  should  first  be  examined  by  the  nitric 
acid  and  stannous  chloride  test.  If  this  yields  a  positive  reaction, 
it  fully  establishes  the  presence  of  the  alkaloid.  When,  however, 
sufficient  material  is  at  hand,  the  reaction  of  this  test  should  be 
confirmed  by  some  of  the  other  tests.  Should  the  nitric  acid  and  tin 
test  fail,  it  is  quite  certain  that,  under  similar  conditions,  the  other 
tests  would  also  fail. 

One  grain  of  brucine  in  solution  was  given  to  a  recently  fed  cat; 
thirty  minutes  afterward,  the  animal  was  seized  with  violent  tetanic 


612  BRUCINE. 

convulsions  and  died  during  the  paroxysm.  On  now  applying  the 
method  directed  for  the  recovery  of  strychnine  to  the  examination 
of  the  contents  of  the  stomach  of  the  animal,  a  very  notable  quan- 
tity of  pure  crystallized  brucine  was  recovered.  And  six  fluid- 
drachms  of  blood,  taken  from  the  same  animal  and  treated  after  the 
strychnine-method,  gave,  when  the  first  chloroform  residue  was  ex- 
amined by  the  tin  test,  perfectly  satisfactory  evidence  of  the  presence 
of  brucine. 

According  to  M.  Pander,  this  alkaloid,  when  taken  into  the 
system,  is  widely  distributed,  and  may  be  found  in  all  the  tissues 
and  fluids  of  the  body,  especially  in  the  liver  and  kidneys;  and 
decomposition  of  the  tissues  for  at  least  three  months  does  not 
destroy  the  brucine. 


ACOXITINE.  G13 


OHAPTEE     IT. 

ACOXITINE,   ATROPINE,   DATURINE. 
Section  I. — Aconitine.     (Aconite.) 

History. — Aconitine,  aconitina,  or  aconitia,  is  the  active  principle, 
or  alkaloid,  of  Aconite,  Monkshood,  or  "Wolfsbane,  the  Aconitum 
Najiellus  of  botanists.  It  exists  in  all  parts  of  the  plant,  but  in  the 
greatest  proportion  in  the  root,  being  combined  with  aconitic  or  equi- 
setic  acid.  The  dried  root  is  usually  estimated  to  contain  from  O.l 
to  0.2  per  cent,  of  the  alkaloid.  Aconitine  was  first  obtained, 
although  in  an  impure  state,  by  Geiger  and  Hesse,  in  1832.  Planta 
assigned  to  the  alkaloid  the  formula  CjoH^-XOy ; 'but,  according  to 
Dr.  C.  R.  A.  Wright,  its  composition  is  €3311^3X012.  In  its  pure 
state  aconitine  is  perhaps  the  most  potent  poison  yet  known.  Ac- 
cording to  Dr.  Wright,  ordinary  aconite  sometimes  contains  another 
alkaloid,  haying  the  composition  C3iH^5NOi,„  named  pieraconitine, 
which  has  a  bitter  taste,  is  uncrystallizable,  and  comparatiyely  inert. 

It  was  formerly  believed  that  the  activity  of  the  diflPerent  species 
of  aconite  was  chiefly  due  to  the  presence  of  the  same  alkaloid — 
namely,  aconitine.  According  to  the  researches  of  Dr.  Wright,  how- 
ever, the  corresponding  crystallizable  principle  in  Aconitum  ferox, 
named  Pseudaconiiine,  has  the  composition  €3^11^9X012 ;  Avhilst  the 
roots  of  Japanese  aconite  owe  their  activity  chiefly  to  Japaconitine, 
C66H^X202i,  these  roots  being  considerably  richer  in  active  crystal- 
lizable principles,  as  also  in  non-crystalline  bases,  than  the  ordinary 
root.  {Jour.  Chem.  Soc,  1877,  403.)  Experiments  would  indicate 
that  in  their  physiological  effects  aconitine,  pseudaconitine,  and  jap- 
aconitine are  at  least  very  similar,  if  not  identical.  So,  also,  the 
three  alkaloids  appear  to  have  the  same  general  chemical  properties. 

Preparation. — Various    methods   have    been    proposed    for   the 


614  ACONITIXE. 

preparation  of  aconitine.  The  following  process  was  advised  by 
MM.  Liegeois  and  Hottot.  The  bruised  root  of  the  plant  is  digested 
for  eight  days  with  rectified  spirit,  slightly  acidulated  with  sulphuric 
acid  ;  the  alcoholic  liquid  is  then  pressed  out,  and  the  alcohol  re- 
moved by  distillation.  The  residue  is  allowed  to  cool,  and  any  solid 
resinous  matter  that  separates  removed.  The  liquid  is  now  concen- 
trated to  the  consistency  of  a  syrup,  then  treated  with  two  or  three 
volumes  of  pure  water,  and  the  mixture  allowed  to  repose,  as  long 
as  any  green  oil  collects  upon  its  surface;  this  is  removed,  the  last 
traces  being  separated  by  a  filter  previously  moistened  with  water. 
The  liquid  is  next  treated  with  slight  excess  of  magnesium  hydrate, 
and  repeatedly  agitated  with  ])ure  ether,  which  will  extract  the  alka- 
loid. The  united  ethereal  extracts  are  evaporated  to  dryness,  and 
the  residue  dissolved  in  water  by  the  aid  of  slight  excess  of  sulphuric 
acid.  The  alkaloid  is  then  precipitated  from  the  filtered  solution  by 
slight  excess  of  ammonia,  and  further  purified  by  repeated  solution 
in  water  acidulated  with  sulphuric  acid  and  re-precipitation  by  am- 
monia. The  final  precipitate  is  washed  with  cold  water  as  long  as 
any  odor  of  ammonia  is  present,  then  dried  at  a  low  temperature. 

According  to  Duquesnel,  crystallized  aconitine  may  be  obtained 
by  the  following  method.  Powdered  aconite  root  is  mixed  with  one 
per  cent,  of  tartaric  acid,  and  extracted  by  three  successive  portions 
of  alcohol.  The  united  and  filtered  liquids  are  distilled  at  a  low 
temperature  to  an  extract,  the  extract  treated  with  water,  and  the 
fatty  and  resinous  matter  separated  by  filtration.  The  filtrate,  which 
contains  the  alkaloid  as  tartrate,  is  repeatedly  shaken  with  ether,  to 
deprive  it  of  coloring  matter;  slight  excess  of  acid  potassium  car- 
bonate is  then  added,  and  the  liberated  alkaloid  extracted  by  ether. 
The  ethereal  liquid  is  shaken  with  a  ten  per  cent,  solution  of  hydro- 
chloric acid,  which  takes  up  the  alkaloid  as  hydrochloride,  the  ex- 
traction with  the  acid  liquid  being  repeated  two  or  three  times  with 
fresh  portions  of  the  liquid.  The  united  acid  liquids  are  saturated 
with  chalk,  then  concentrated  at  a  gentle  heat,  filtered,  and,  while 
still  warm,  mixed  with  a  strong  solution  of  sodium  nitrate.  This 
mixture  is  allowed  to  cool  slowly,  when  the  alkaloid,  in  the  form 
of  nitrate,  will  separate  in  its  crystalline  state.  The  nitrate  thus 
obtained  is  dissolved  in  water,  the  solution  treated  with  slight  excess 
of  acid  potassium  or  ammonium  carbonate,  and  the  freed  alkaloid 
extracted  by  chloroform.     On  evaporation,  the  chloroform  will  leave 


PiiYsroy.oniCAT.  effects.  G15 

a  syrupy  liquid,  which  will  soon  crystallize,  especially  if"  the  syrup 
be  treated  with  an  e(iual  voUunc  of  {dcohol. 

The  total  quantity  of  active  alkaloids  obtained  from  aconite  root 
has  varied  greatly,  de|)ending  upon  the  process  followed  for  the  ex- 
traction, the  product  ranging,  according  to  M,  Schneider,  from  0.002 
to  0.34  j)er  cent,  of  the  root.  So,  also,  great  variation  exists  in 
the  strength  of  samples  of  the  alkaloid  as  foiitid  in  the  shops. 
From  a  coin])arativc  examination  of  some  of  the  well-known  com- 
mercial preparations  of  aconitine.  Prof.  P.  C.  Plugge  concluded 
that  Petit's  nitrate  has  a  toxic  action  at  least  eight  times  greater 
than  that  of  ^Nferck,  and  one  hundred  and  seventy  times  greater  than 
that  of  Friedliinder.  Morson's  aconitine  is  said  to  be  about  equal 
in  activity  to  that  of  Petit. 

Poisoning  by  aconitine  in  its  j^ure  slate  has  been  of  rare  occur- 
rence; but  there  have  been  numerous  instances  of  poisoning  by  the 
root,  leaves,  and  some  of  the  preparations  of  aconite,  chiefly,  how- 
ever, as  the  result  of  accident.  The  root  has  not  unfrequently  been 
mistaken  for  horseradish.  The  principal  pharmaceutical  prepara- 
tions of  aconite  are  the  tincture  of  the  root  and  the  alcoholic  extract. 
Each  of  these  preparations  is  subject  to  considerable  variation  in 
strength,  depending  both  on  the  formula  followed  for  its  prei)aration 
and  on  the  quality  of  the  material  employed.  The  medicinal  dose 
of  the  pure  alkaloid  is  said  to  be  about  the  l-130th  of  a  grain :  it 
is  rarely  prescribed  in  this  form,  and  requires  great  caution  in  its 
administration. 

Symptoms. — The  effects  of  poisonous  doses  of  aconite  are  in 
some  respects  quite  peculiar.  At  first  there  is  a  sense  of  tingling 
and  numbness  in  the  lips,  mouth,  and  throat,  with  a  feeling  of 
warmth  or  burning  in  the  stomach.  These  effects  are  succeeded  by 
tingling  in  various  parts  of  the  body,  pain  in  the  abdomen,  headache, 
vertigo,  and  nausea,  frequently  attended  by  vomiting,  and  sometimes 
purging;  there  is,  also,  diminished  sensibility  of  the  skin,  constric- 
tion in  the  throat,  frothing  at  the  mouth,  partial  or  entire  loss  of 
voice,  impaired  vision,  ringing  in  the  ears,  a  feeling  of  tightness  in 
various  parts  of  the  body,  cold  perspirations,  muscular  tremors,  and 
great  prostration  of  strength.  The  pulse  becomes  small  and  feeble, 
or  altogether  imperceptible;  the  countenance  pale  and  sunken;  the 
extremities  cold  and  clammy  :  the  pupils  are  usually  dilated,  but  not 


616  ACONITINE. 

unfreqnently  contracted.  Death  usually  takes  place  by  syncope. 
In  some  instances  death  is  preceded  by  delirium  and  convulsions. 
In  fifty-three  cases  of  aconite  poisoning  collected  by  Dr.  Tucker,  of 
New  York,  general  convulsions  occurred  only  in  seven  ;  and  in 
forty-one  cases  collected  by  Dr.  E.  T.  Reichert  {3Ied.  Times,  Nov. 
1881,  105),  general  convulsions  were  present  only  in  three  instances. 

The  symptoms  usually  manifest  themselves  within  a  few  minutes 
after  the  ])oison  has  been  taken ;  but  they  have  been  delayed  for 
more  than  an  hour,  and  in  one  case  for  even  more  than  three  hours. 
In  a  case  quoted  by  Dr.  Beck  {Bled.  Jur.,  ii.  890),  in  which  a  man 
had  eaten  some  salad  containing,  by  mistake,  a  quantity  of  aconite, 
the  patient  immediately  experienced  a  burning  heat  in  the  tongue  and 
gums,  and  irritation  in  the  cheeks.  This  tingling  sensation  extended 
over  the  whole  body,  and  was  accompanied  by  muscular  twitchings. 
The  eyes  and  teeth  became  fixed ;  the  extremities  cold  and  bathed 
with  perspiration ;  the  pulse  imperceptible,  and  the  breathing  so 
short  as  scarcely  to  be  distinguishable.  Under  the  active  use  of 
remedies  the  patient  gradually  recovered.  In  another  case,  a 
woman  on  swallowing  an  alcoholic  tincture  of  the  root  immediately 
experienced  a  tingling  sensation  in  her  lips,  mouth,  and  tongue;  her 
teeth  felt  as  if  loose,  and  her  lower  jaw  as  if  dead.  Tingling  then 
began  in  her  fingers  and  extended  all  over  her  body,  and  she  felt 
numb.     She  finally  recovered.     [Med.  Times,  Feb.  1879,  241.) 

In  a  case  reported  by  Dr.  Gray,  in  which  a  healthy  boy,  fourteen 
years  of  nge,  Avas  given  by  mistake  a  tablespoonful  of  the  tincture 
of  aconite,  the  following  symptoms  were  observed.  In  about  five 
minutes  the  patient  began  to  experience  the  effects  of  the  poison, 
and  in  twenty  minutes  the  pupils  were  slightly  dilated  and  nearly 
insensible  to  light ;  the  countenance  was  pale,  and  he  moved  with 
difficulty;  his  head  felt  heavy,  and  there  was  frequent  retching, 
with  the  discharge  of  small  quantities  of  mucus.  An  emetic  of 
zinc  sulphate  was  immediately  administered,  and  quickly  produced 
copious  vomiting.  The  patient  now  experienced  a  sense  of  intense 
burning  in  the  stomach  and  oesophagus,  and  was  greatly  prostrated ; 
the  pulse  became  slow,  the  extremities  cold,  the  pupils  widely  dilated, 
and  he  complained  of  great  numbness  of  his  head,  but  not  of  any 
other  part  of  the  body,  and  lost  the  power  of  sight.  Under  the  use 
of  a  laxative  enema,  and  external  and  internal  stimulants,  there  was 
a  slight  amelioration  of  the  symptoms  for  about  half  an  hour ;  but 


FATAL    PKHIOD.  01  7 

the  collapse  again  retiinicil,  the  rcsj)iration  became  slow  and  diflicMilt, 
iho  muscles  of  tlic  iicnd  and  trunk  ri<:;id,  the  surface  cold,  deglutition 
imposslMc,  and  death  su|»ervcncd  suddcidy,  under  full  consciousness, 
two  hours  after  the  poison  had  been  taken.  {New  York  Jour,  of 
Med.,  Nov.  1848,  33G.) 

In  another  case,  a  healthy  man  ate  some  greens  consfstiiig  for  the 
most  part  of  the  root  of  aconite.  Almost  immediately  afterward 
he  complained  of  a  feeling  as  if  he  could  not  draw  in  his  tongue, 
and  various  hallucinations  of  sight.  These  symptoms  were  soon 
succeeded  by  vomiting,  involuntary  stools  and  passage  of  urine,  a 
peculiar  sensation  in  the  extremities,  a  feeling  of  pricking  in  the 
whole  body,  and  fainting,  followed  by  death.  [ReiCs  Monograph 
upon  Aconite,  46.) 

The  following  case  of  recovery  occurred  in  the  practice  of  Dr. 
McCready,  of  New  York.  A  healthy  Irishwoman,  about  twenty- 
five  years  of  age,  swallowed  a  tablespoonful  of  a  saturated  tincture 
of  aconite,  mistaking  it  for  brandy.  When  seen  an  hour  afterward, 
her  countenance  was  flushed,  the  pupils  dilated,  though  sensible  to 
light;  the  pulse  frequent,  soft,  and  weak,  the  beat  being  sometimes  so 
feeble  as  to  be  almost  imperceptible.  She  complained  of  a  feeling 
of  fulness  about  her  limbs,  as  if  they  were  about  -to  burst,  accom- 
panied by  a  sensation  of  numbness  and  pricking  over  the  whole  sur- 
face; and  there  were  numbness  and  tingling  of  the  tongue,  and  a 
strange  sensation  about  the  throat.  There  was  no  sickness  at  the 
stomach,  and  the  head  was  perfectly  clear.  An  emetic  of  zinc 
sulphate  and  ipecacuanha  was  administered,  and  produced  copious 
vomiting.  Half  an  hour  afterward,  the  pulse  was  still  frequent  and 
feeble,  the  beats  continuing  irregular  in  force.  She  complained  of  feel- 
ing weak,  but  in  other  respects  was  about  the  same  as  when  tirst  seen. 
Three  hours  later,  the  dilatation  of  the  pupils  had  passed  away,  but 
the  numbness  and  tingling  remained.  The  next  day  she  was  almost 
in  her  usual  health.     [Amer.  Jour.  3Ied.  Sci,  Jan.  1852,  268.) 

Period  ivhen  Fatal. — In  fatal  poisoning  by  aconite  or  any  of  its 
preparations,  death  usually  occurs  in  from  two  to  six  hours  after  the 
poison  has  been  taken  ;  but  considerable  variation  has  been  observed 
in  this  respect. 

In  a  case  communicated  to  me  by  Prof.  L.  McLane  Tiffany,  of 
Baltimore,  two  drachms  of  the  tincture  of  the  root  proved  fatal  to 
a  healthy  woman,  aged  thirty-four  years,  in  forty-five  minutes  after 


618  ACOXITIXE. 

the  poison  was  taken.  In  another  case,  a  lotion  containing  com- 
pound liniment  of  aconite  and  belladonna,  swallowed  by  mistake, 
caused  the  death  of  a  man,  under  most  violent  symptoms  of  aconite 
poisoning,  in  about  thirty  minutes.    {British  Med.  Jour.,  ]  882,  i.  774.) 

A  case  is  also  reported  in  which  one  drachm  of  the  tincture, 
taken  by  an  adult,  proved  fatal  in  one  hour  and  a  half,  the  patient 
being  strongly  convulsed  just  before  death.  In  another  instance,  a 
child,  aged  two  years  and  seven  months,  having  eaten  an  unknown 
quantity  of  the  fresh  leaves  of  aconite,  was  soon  seized  with  violent 
symptoms,  but  death  did  not  occur  until  after  the  lapse  of  about 
twenty  hours.  {Lancet,  London,  June,  1856,  715.)  In  this  case, 
shortly  after  the  symptoms  manifested  themselves  there  was  violent 
vomiting,  which  brought  away  pieces  of  the  leaves:  no  vegetable 
matter  was  found  in  the  stomach  after  death. 

In  a  series  of  six  fatal  cases  of  aconite  poisoning  communicated 
to  me  by  Prof.  J.  W.  Mallet,  which  occurred  in  the  Western  Lu- 
natic Asylum  of  Virginia,  in  1883,  death  took  place  respectively 
within  eight  minutes,  ten  minutes,  thirteen  to  fifteen  minutes,  one  hour 
and  a  quarter,  two  hours  and  a  quarter,  and  in  four  days  after  the 
poison  had  been  taken.  Two  other  patients  that  had  taken  the 
poison  fully  recovered.  The  poison,  either  in  the  form  of  the  al- 
kaloid or  of  a  very  concentrated  solution  of  aconite,  had  been,  in 
some  manner  not  ascertained,  introduced  into  the  several  medicines 
given  to  these  patients.  Prof.  Mallet  readily  detected  acouitine  in 
the  contents  of  the  stomach  of  three  of  the  patients,  and  also,  in  one 
instance,  in  the  dregs  of  the  medicine  administered :  these  were  the 
only  chemical  examinations  made  in  these  cases. 

Fatal  Quantity. — Since  the  preparations  of  aconite  are  subject 
to  great  variation  in  strength,  similar  quantities  of  the  same  form 
of  preparation  have  given  rise  to  very  different  results.  Thus,  Dr. 
Fleming  mentions  an  instance  where  two  grains  of  the  alcoholic 
extract  occasioned  alarming  effects,  and  another  in  which  four  grains 
proved  fatal ;  whilst  Dr.  Christison  relates  an  instance  in  which  he 
gave  six  grains  of  a  carefully  prepared  alcoholic  extract  to  a  woman 
suffering  from  rheumatism,  without  being  able  to  observe  any  effect 
whatever.  {On  Poisons,  667.)  In  a  case  reported  by  Dr.  Easton, 
twenty-five  minims  of  a  tincture  of  the  root  of  aconite,  with  twenty 
minims  of  tincture  of  belladonna,  caused  the  death  of  a  healthy 
young  man  within  three  hours ;  and  in  another  instance  twenty-five 


FATAL   QUANTITY.  C19 

drops  of  the  tincture,  i)rescribecl  tlirou<;li  ijjiiorance,  proved  fatal  to 
a  mail  in  about  four  lioui-s.  {American  Medical  Monlhlij,  Alardi, 
1854,  223.)  Several  instances  are  reported  in  which  about  a  drachm 
of  the  tincture  destroyed  life. 

In  a  case  communicated  to  Dr.  Pereira,  two  d<jses  of  six  drops 
each  of  the  tincture,  taken  at  an  interval  of  two  hours,  by  a  young 
man  aired  twenty-one  years,  produced  most  alarming  symptoms. 
{Mat.  Med.,  ii.  1091.)  We  are  acquainted  with  an  instance  in  which 
a  verv  intelligent  physician  administered  to  his  wife  a  dose  of  five 
drops  of  Thayer's  fluid  extract  of  the  root  of  aconite.  In  from  ten 
to  fifteen  minutes  afterward  she  experienced  a  burning  sensation  in 
the  throat  and  great  numbness  in  the  arms;  these  effects  were  soon 
followed  by  tingling  in  the  surface  of  the  whole  body,  difficulty  of 
breathing,  impending  suffocation,  dimness  of  j/ision,  and  alarming 
prostration,  which  continued  for  about  two  hours  :  she  then  rapidly 
recovered. 

Kecoverv  has  not  unfrequently  taken  place  after  comparatively 
large  quantities  of  some  of  the  preparations  of  aconite  were  taken. 
In  a  case  reported  by  Mr.  Kay,  a  lady  took  by  mistake  two  tea- 
spoonfuls  of  the  tincture,  and  entirely  recovered  in  eight  hours 
afterward.  In  this  case  the  symptoms  did  not  manifest  themselves 
until  an  hour  after  the  poison  had  been  taken.  An  emetic  was  then 
given,  which  quickly  operated.  The  patient  then  lost  the  use  of  her 
lower  extremities ;  the  face  had  an  anxious  expression ;  the  forehead 
was  wrinkled  and  corrugated;  the  pupils  slightly  dilated;  pulse 
slow,  feeble,  and  intermitting;  the  extremities  cold,  but  the  intellect 
quite  unaffected.  She  complained  of  a  burning  sensation  in  the 
throat  and  a  constriction  at  the  chest ;  and  lost  the  sense  of  feeling 
in  her  legs,  arms,  and  face.  {Lancet,  Eeprint,  Oct.  1861,  273.)  In 
another  case,  related  by  M.  Devay,  a  porter  in  a  druggist's  shop 
swallowed  by  mistake  nearly  one  ounce  and  a  half  of  an  alcoholic 
solution  of  aconite,  and  although  he  immediately  experienced  a  sense 
of  heat  and  constriction  in  the  throat  and  was  soon  seized  with  the 
most  violent  symptoms,  yet  he  was  quite  well  three  days  afterward. 
{Chemical  Gazette,  ii.  220.) 

Aconitine  in  its  pure  state,  as  already  mentioned,  is  one  of  the 
most  virulent  poisons  known.  Dr.  Headland  considers  that  one- 
tenth  of  a  grain  of  the  pure  alkaloid  would  be  sufficient  to  destroy 
the  life  of  a  healthy  adult   man.     And   Dr.   Pereira   mentions  an 


620  ACONITINE. 

instance  in  which  one-fiftieth  of  a  grain  nearly  proved  fatal  to  an 
elderly  lady.  {Mat.  Med.,  ii.  1093.)  A  most  remarkable  instance 
of  recovery,  in  which  a  gentleman  had  taken  two  grains  and  a  half 
of  aconitine,  is  related  by  Dr.  Golding  Bird.  It  seems  that  almost 
immediately  after  taking  the  poison  the  patient  fell,  and  was  seized 
with  violent  vomiting,  by  which  it  is  believed  that  most  of  the 
poison  was  ejected.  Some  time  after  the  occurrence,  the  patient  was 
in  a  most  fearful  state  of  collapse ;  the  surface  cold  and  perspiring ; 
the  action  of  the  heart  scarcely  perceptible,  but  the  intellect  was 
unimpaired.  The  most  prominent  symptom,  which  continued  for 
some  hours,  was  repeated  and  most  violent  convulsive  vomiting. 
On  attempting  to  swallow  any  fluid  the  patient  was  seized  with 
violent  spasms  of  the  throat,  somewhat  similar  to  those  observed  in 
hydrophobia.  This  jatter  symptom  continued  for  several  hours,  and 
it  was  not  until  about  thirty  hours  after  the  poison  had  been  taken 
that  the  patient  was  considered  convalescent.  [Neio  York  Journal  of 
Medicine,  March,  1848,  285.) 

Three  cases  of  poisoning  by  aconitine  nitrate,  one  of  them  fatal, 
are  reported  by  Dr.  A.  Busscher.  [Berl.  Klin.  WochenscJir.,  June, 
1880,  337.)  In  one  of  these,  a  feeble  man,  aged  sixty-one  years, 
suffering  from  chronic  bronchitis,  took,  at  the  advice  of  a  physician, 
five  drops  of  a  solution  containing  about  l-165th  grain  (0.4  milli- 
gramme) of  the  nitrate.  The  patient  immediately  experienced  a 
feeling  of  constriction  and  burning  in  the  mouth,  extending  to  the 
stomach ;  he  then  felt  cold,  and  laid  himself  upon  a  bed.  Two  hours 
later,  he  took  twenty  drops  of  the  solution,  and  this  dose  was  repeated 
except  the  last,  which  contained  only  ten  drops,  so  that  during  a 
period  of  about  two  days  he  took  in  all  seven  doses,  equivalent  to  about 
l-7th  grain  (9.2  milligrammes)  of  the  nitrate.  After  each  dose  he  ex- 
perienced violent  symptoms  of  aconite  poisoning,  so  that  at  one  time 
it  was  believed  he  would  certainly  die;  but  he  finally  recovered. 

Dr.  Carl  Meyer,  who  prescribed  the  medicine  in  the  foregoing 
case,  swallowed  from  fifty  to  sixty  drops  of  the  same  solution,  equal 
to  about  l-16th  grain  (4  milligrammes)  of  the  aconite  salt.  At  the 
end  of  fifteen  minutes  symptoms  of  poisoning  began  to  manifest 
themselves.  About  four  hours  later,  his  face  was  pale,  the  pulse 
small  and  irregular,  skin  cold,  pupils  contracted,  and  there  was  a 
sense  of  burning  in  the  mouth,  with  constriction  of  the  throat, 
extending  to  the  abdomen.     He  complained  of  precordial  distress, 


TREATMENT.  G'21 

and  a  sense  of  heaviness  aiul  feebleness  in  tiic  extremities,  especially 
in  the  legs.  The  pupils  suddenly  dilated,  and  sight  was  lost,  but 
again  returned  when  the  pupils  became  contracted.  Irritation  of 
the  pharynx  induced  vomiting.  Convulsions  now  appeared,  attended 
with  congestion  of  the  head,  and  labored,  stertorous  respiration. 
He  complained  of  deafness  and  ringing,  first  in  one  and  then  in  the 
other  ear.  After  a  subcutaneous  injection  of  ether  the  pupils  again 
dilated,  and  vision  was  lost ;  vomiting  again  came  on,  and  was 
followed  by  violent  and  prolonged  convulsions.  He  then  became 
unconscious,  the  pupils  insensible  to  light,  the  respiration  labored, 
and  the  heart  gradually  failing,  death  took  place  five  hours  after  the 
ingestion  of  the  poison.     {Ann.  cVHyg.,  Jan.  1882,  87.) 

In  these  cases,  as  also  in  a  third,  which  did  not  prove  fatal, 
Petit's  crystallized  aconitine  nitrate  was  taken ;  whereas  Dr.  JNIeyer 
intended  that  Friedliinder's  preparation  should  be  administered,  the 
former  being,  according  to  Plugge,  170  times  more  active  than  the 
latter. 

In  a  remarkable  case  tried  in  England  in  1882,  in  which  George 
Lamson,  a  medical  practitioner,  was  convicted  of  the  murder  of  his 
brother-in-law,  Percy  Malcolm  John,  by  the  administration  of  per- 
haps two  grains  of  aconitine  enclosed  in  a  gelatine  ca])sule,  the 
following  symptoms  were  present,  as  reported  by  Dr.  Thos.  Steven- 
son. [Guy^s  Hosp.  Rep.,  1883,  307.)  Half  an  hour  after  taking  the 
capsule  Percy  complained  of  heart-burn,  and  a  little  later  said  that 
he  felt  as  he  had  felt  on  a  former  occasion  when  Lamson  had  given 
him  a  quinine  pill.  After  this  he  complained  that  his  skin  felt  all 
drawn  up,  and  that  his  mouth  was  very  painful.  Violent  vomiting 
ensued,  and  he  threw  himself  about  most  violently;  there  was  great 
pain  in  the  region  of  the  stomach,  and  a  sense  of  constriction  in  the 
throat,  with  inability  to  swallow.  He  was  so  restless  and  violent 
that  it  required  great  force  to  restrain  him.  The  pain  was  incessant 
till  near  the  time  of  his  death.  Finally  he  became  unconscious,  his 
breathing  became  slower  and  sighing,  the  heart's  action  weaker,  and 
he  died  four  hours  and  five  minutes  after  taking  the  capsule. 

In  another  case,  quoted  by  Dr.  Stevenson  [Ibid.),  a  chemist 
with  suicidal  intent  took  eight  grains  of  Merck's  aconitine.  In  half 
an  hour  violent  symptoms  appeared,  and  death  took  place  twelve 
hours  after  the  poison  had  been  taken. 

Treatment. — In  poisoning  by  aconite  or  its  active  alkaloid,  the 


622  ACONITIXE. 

first  indication  is  to  evacuate  thoroughly  the  contents  of  the  stomach, 
either  by  an  emetic  or  the  use  of  the  stomach-pump.  As  an  emetic 
zinc  sulphate  is  usually  preferred.  Stimulants,  such  as  ammonia 
and  brandy,  may  often  be  employed  with  great  advantage;  and  the 
use  of  stimulating  injections  has  been  attended  with  good  results. 
As  an  antidote,  the  free  administration  of  finely-powdered  animal 
charcoal,  mixed  with  water,  has  been  strongly  recommended  by  Dr. 
Headland  and  others.  It  is  claimed  that  this  substance  will  unite 
with  the  poisonous  alkaloid,  and  thus  prevent  its  absorption  into  the 
system.  The  charcoal  is  then  removed  from  the  stomach  by  an 
emetic.  Vegetable  infusions  containing  tannic  acid,  and  also  a  solu- 
tion of  iodine  in  potassium  iodide,  have  been  strongly  advised,  on 
the  ground  that  they  form  insoluble  compounds  with  the  alkaloid. 

From  the  apparent  antagonism  existing  between  the  physiologi- 
cal effects  of  aconite  and  those  of  nux  vomica,  these  substances  have 
been  recommended  as  mutual  antidotes.  The  following  case,  in 
wdiich  this  remedy  was  employed,  is  reported  by  Dr.  Hanson.  A 
boy,  aged  five  years,  swallowed  a  mixture  of  tincture  of  aconite 
and  simple  syrup.  When  first  seen  by  Dr.  Hanson,  the  patient 
was  laboring  under  the  usual  symptoms  of  aconite  poisoning,  in  an 
aggravated  degree.  Emetics  and  tickling  the  fauces  with  a  feather 
were  resorted  to,  but  without  producing  vomiting,  and  the  patient 
continued  to  sink.  Half  an  hour  after  the  first  dose  of  tartar  emetic 
had  been  given,  three  drops  of  the  tincture  of  nux  vomica  were 
administered.  In  a  few  minutes  the  action  of  the  heart  was  in- 
creased in  force,  and  the  respiration  much  improved.  At  the  end 
of  twenty  minutes,  the  dose  of  nux  vomica  was  repeated.  Vigorous 
vomiting  now  soon  ensued,  after  which  the  patient  rapidly  recov^ered. 
{Amer.  Jour.  Med.  ScL,  Jan.  1862,  285.) 

As  a  remedy  in  poisoning  by  aconite.  Dr.  J.  M.  Fothergill  ad- 
vised the  use  of  digitalis.  And  in  a  case  reported  by  Dr.  W.  Dobie 
[British  3Ied.  Jour.,  Dec.  1872,  682),  in  which  the  patient  had  taken 
an  ounce  of  Fleming's  tincture  of  aconite,  a  subcutaneous  injection 
of  twenty  minims  of  tincture  of  digitalis  was  administered.  At  the 
end  of  twenty  minutes  the  patient  began  to  rally,  and  was  soon  able 
to  swallow  a  teaspoonful  of  the  tincture  mixed  with  ammonia  and 
brandy.  This  mixture  was  twice  repeated  within  an  hour,  and  the 
patient  rapidly  recovered.  Dr.  P.  Hooper  has  recently  reported 
(il/eri.  Times,  Feb.  1883,  328)  two  cases  of  accidental  aconite  poison- 


PATHOLOGICAL   EFFECTS.  G2:^> 

ing  ill  wliicli  lie  oniploycd  repeated  draclini  doses  of  tincture  of 
dijjjitMlis  with  trivat  advantaj^e. 

PosT-MOKTKM  A I'l'HARAN'CES. — Tlic  iiiost  comtiioii  morbid  ap- 
pearances, ill  death  from  aconite,  are  an  injected  condition  of  the 
l)h)od-vessels  of  the  brain  and  of  its  membranes,  and  contrestion  of 
the  lungs  and  liver,  with  more  or  less  redness  of  the  mucous  mem- 
brane of  the  stomach  and  intestines.  The  stomach  and  small  intes- 
tines are  frequently  found  empty.  The  right  cavities  of  the  lieart 
usually  contain  more  or  less  blood  ;  the  blood  throughout  the  body 
is  generally  fluid  and  of  a  dark  color.  It  need  hardly  be  remarked 
that  none  of  these  appearances  are  peculiar  to  death  from  this  sub- 
stance. In  two  cases  of  fatal  poisoning  by  a  tincture  of  the  root  of 
aconite,  quoted  by  Dr.  Beck,  the  only  morbid  appearances  observed 
on  dissection  were  great  redness  of  the  lining  membrane  of  the 
stomach  and  small  intestines. 

In  au  instance  quoted  by  Orfila  {Toxicologie,  ii.  443),  in  which 
five  persons  swallowed  each  a  glass  of  brandy  in  which  the  root  of 
aconite  had  been  macerated,  and  three  of  them  died,  death  taking 
place  in  about  two  hours,  the  following  appearances  were  observed. 
The  cesophagus,  stomach,  and  intestines  were  found  much  inflamed, 
and  the  blood-vessels,  especially  the  veins,  of  the'  digestive  tube 
much  injected.  The  mesentery  was  also  inflamed.  The  cavity  of 
the  peritoneum  contained  a  large  quantity  of  yellowish  serum.  The 
lungs  were  dense,  of  a  bluish  and  violet  hue,  slightly  crepitant,  and 
gorged  with  blood.  The  pericardium  contained  a  large  quantity  of 
serum  ;  the  heart  and  large  vessels  presented  nothing  remarkable. 
The  brain  was  healthy,  but  its  blood-vessels  somewhat  injected. 

In  the  case  of  the  child,  already  cited,  in  which  the  leaves  of 
aconite  had  been  eaten  and  life  was  prolonged  for  about  twenty 
hours,  the  body  presented  the  following  appearances  sixty  hours 
after  death.  The  abdomen  externally  was  much  discolored;  and 
patchy  discolorations  were  visible  on  the  thighs  and  legs,  but  the 
spots  were  not  so  apparent  as  during  life.  The  stomach  was  highly 
inflamed  throughout  its  whole  extent;  it  contained  a  little  fluid  of  a 
lightish-brown  color,  but  no  food,  nor  any  traces  of  leaves  or  other 
vegetable  matter.  Various  parts  of  the  small  intestines  presented 
patches  of  intense  inflammation,  in  some  places  approaching  to 
gangrene.  The  large  intestines  presented  nothing  particular.  The 
bladder  was  full  of  urine ;  the  spleen  somewhat  congested.    The  peri- 


624  ACONITINE. 

cardium  contained  about  half  an  ounce  of  bloody  serum.  The  heart 
was  full  of  uncoagulated  blood,  and  the  blood  throughout  the  body- 
was  thin  and  fluid.  The  other  parts  of  the  body  were  nearly  or  al- 
together normal. 

In  the  case  of  Dr.  Meyer,  who  had  taken  the  nitrate  of  aconitine, 
there  was  found  great  paleness  of  the  body,  and  the  pupils  were 
somewhat  dilated.  The  stomach,  lungs,  and  especially  the  small 
intestines,  were  much  congested  ;  but  the  colon  and  rectum  were  pale, 
as  was  also  the  bladder.  The  heart  was  dilated,  and  the  right  side 
contained  a  little  liquid  blood.  The  vessels  of  the  membranes  of 
the  brain  were  distended,  and  at  certain  points  exudations  under  the 
arachnoid  were  present;  the  ventricles  contained  a  bloody  serous 
effusion,  and  there  was  a  bloody  exudation  on  the  choroid  plexus. 
The  blood  throughout  the  body  was  liquid  and  of  a  bright  cherry- 
red  color. 

In  the  Lamson  case,  sixty-four  hours  after  death,  the  pupils  were 
dilated,  and  the  lips  pale,  as  was  also  the  tongue.  The  membranes 
of  the  brain  and  the  brain  itself  were  slightly  congested.  The  lungs, 
liver,  spleen,  and  kidneys  were  more  or  less  congested.  The  heart 
was  very  flaccid,  and  its  cavities  almost  empty.  The  mucous  mem- 
brane of  the  stomach  was  congested  throughout,  and  presented  in 
places  small,  slightly  raised,  yellowish-gray  patches.  The  stomach 
contained  three  or  four  ounces  of  fluid.  The  first  portion  of  the 
duodenum  was  greatly  congested,  and  patches  of  congestion  were 
present  in  other  parts  of  the  small  intestine.  The  bladder  contained 
three  or  four  fluid-ounces  of  urine.     {Guy^s  Hosp.  Rep.,  xxvi.  312.) 

Chemical  Properties. 

In  the  Solid  State. — Aconitine,  in  its  pure  state,  is  a  trans- 
parent, odorless  solid,  Avhich  crystallizes  with  difficulty,  forming 
either  colorless  rhombic  or  hexagonal  tables,  or  small  four-sided 
prisms.  It  has  an  acrid  taste,  followed  by  a  sense  of  tingling  and 
numbness  of  the  tongue ;  applied  in  the  form  of  solution  to  the 
skin,  it  causes  a  persistent  feeling  of  heat  and  numbness.  These 
effects  are  produced  by  even  extremely  minute  quantities  of  the 
alkaloid.  Applied  in  the  form  of  ointment  to  the  eye,  it  causes 
much  the  same  effects,  with,  according  to  Dr.  Pereira,  contraction  of 
the  pupil.  Aconitine  is  unchanged  by  exposure  to  the  air.  When 
moderately  heated  in  a  tube,  it  fuses  to  a  transparent  liquid,  which, 


CHEMICAL   PROPERTIES.  G25 

as  the  lieat  is  increased,  becomes  brown,  then  black,  and  is  finally 
rcducod  to  a  solid  carbonaceous  mass.  Heated  in  the  air  on  a  i)icce 
of  j)<)rcehiin,  it  undergoes  a  similar  chanire,  and  leaves  a  black  cinder, 
which  is  but  slowly  consumed.  According  to  Dr.  Guy,  aconitine 
melts  at  G0°  C.  (140°  F.),  and  at  204.4°  C.  (400°  F.)  yields  subli- 
mates which  are  amorphous. 

As  found  in  the  shops,  aconitine  is  usually  amorphous  and  more 
or  less  colored,  and  very  variable  in  strenjjth,  some  of  the  samples 
being  almost  wholly  inert.  Dr.  Pereira  states  that  he  met  with  a 
French  preparation  of  which  he  took  one  grain  without  perceiving 
the  least  effect  either  on  the  tongue  or  otherwise.  And  of  three 
samples  prepared  by  different  German  manufacturers  that  we  have 
examined,  one  contained  only  a  mere  trace  of  the  alkaloid,  and 
the  other  two  appeared  to  consist  entirely  of  foreign  matter.  The 
aconitine  prepared  by  Mr.  Morson  is  usually  in  the  form  of  a  dull 
white  powder,  consisting  chiefly  of  small  granules  and  thin,  trans- 
parent plates.  This  manufacturer,  Mr.  Grov^es,  and  others,  have 
obtained  the  alkaloid  in  the  form  of  large,  well-defined  crystals.  A 
sample  of  Duquesnel's  aconitine  in  our  possession  is  in  the  form 
of  large,  colorless  crystals,  many  of  them  weighing  about  1-lOth 
grain  each. 

Aconitine  has  strongly  basic  properties,  completely  neutralizing 
acids  to  form  salts,  several  of  which  have  been  obtained  in  the  crys- 
talline form.  When  touched  in  the  drv  state  with  concentrated  sul- 
phuric  acid,  jjure  aconitine  slowly  dissolves,  without  any  coloration 
whatever,  to  a  colorless  solution,  which  remains  unchanged  for  many 
hours.  A  small  crystal  of  potassium  nitrate  stirred  in  a  sulphuric 
acid  solution  of  the  alkaloid  produces  no  visible  change,  even  on 
the  application  of  a  moderate  heat;  if  a  crystal  of  potassium  dichro- 
mate  be  stirred  in  the  solution,  the  mixture  slowly  acquires  a  green 
color,  due  to  the  separation  of  chromium  sesquioxide.  Concentrated 
nitric  acid  dissolves  the  alkaloid  to  a  colorless  solution,  which  is  un- 
changed by  a  moderate  heat,  and  by  a  solution  of  stannous  chloride. 
The  alkaloid  is  also  dissolved  to  a  colorless  solution  by  hydrochloric 
acid. 

SoJuhility. — When  excess  of  Morson's  aconitine  is  kept  in  contact 
with  imre  icater  at  a  temperature  of  about  15.5°  C.  (60°  F.)  for  ten 
hours,  one  part  dissolves  in  1783  parts  of  the  fluid.  On  evaporating 
the  solution  to  dryness,  the  alkaloid  is  left  in  the  form  of  a  hard, 

40 


626  ACONITINE. 

transparent,  colorless,  vitreous  mass,  which,  when  broken  up,  presents 
the  appearance  of  crystalline  plates.  The  recently  precipitated  alka- 
loid is  much  more  soluble  in  water  than  just  stated.  A  sample 
of  DuquesneFs  crystallized  aconitine  had  about  the  same  degree  of 
solubility  in  water  as  that  of  Morson.  Absolute  ether  kept  in  contact 
with  excess  of  aconitine  for  several  hours,  at  the  ordinary  tempera- 
ture, takes  up  one  part  in  777  parts  of  the  menstruum.  On  allowing 
the  solution  to  evaporate  spontaneously,  the  alkaloid  is  left  as  a 
transparent  glacial  mass.  Chloroform  readily  dissolves  the  alkaloid 
in  nearly  every  proportion,  and  leaves  it  on  spontaneous  evapora- 
tion in  the  form  of  a  vitreous  mass.  It  is  also  freely  soluble  in 
alcohol.  The  salts  of  aconitine  are,  with  few  exceptions,  readily 
soluble  in  water.  They  are  also  soluble  in  alcohol,  but  insoluble 
in  ether. 

Of  Solutions  of  Aconitine. — In  the  following  investigations 
in  regard  to  the  behavior  of  solutions  of  aconitine,  pure  aqueous 
solutions  of  the  hydrochloride  were  employed.  The  fractions  in- 
dicate the  fractional  part  of  a  grain  of  the  pure  alkaloid  present 
in  one  grain  of  liquid ;  and,  unless  otherwise  stated,  the  results  refer 
to  the  behavior  of  one  grain  of  the  solution. 

1 .    The  Caustic  Alkalies. 

The  fixed  caustic  alkalies  and  ammonia  throw  down  from  some- 
what concentrated  solutions  of  salts  of  aconitine  a  dirty-white,  floccu- 
lent  precipitate  of  the  hydrate  of  the  alkaloid,  which  is  nearly  wholly 
insoluble  in  excess  of  the  precipitant,  but  readily  soluble  in  free  acids, 
even  acetic  acid. 

1.  YQ-g-  grain   of  aconitine,  in   one  grain  of  water,  yields  a  rather 

copious  precipitate,  which  is  insoluble  in  large  excess  of  the 
reagent. 

2.  -g-^-g-  grain  yields  a  quite  good  precipitate,  which  dissolves,  not 

readily,  however,  in  several  drops  of  the  precipitant. 

3.  YWo"  g^^^i"  •  1^0  satisfactory  indication. 

The  alkali  carbonates  fail  to  produce  a  precipitate  with  a  1-1 00th 
solution  of  the  alkaloid. 

2.  Auric  Chloride. 

Trichloride  of  gold  produces  in  solutions  of  salts  of  aconitine, 
even  when  highly  diluted,  a  yellow,  amorphous  precipitate,  consisting 


BROMINE    IX    BROMOIIYDRIC   ACID    TEST.  G27 

of  ncoiiitinc   liydroclilorido   and   aiiric;  oldorido,  which    is  hiil  very 
sparingly  sohihlc  in  hydrochloric  acid. 

1.  Ykfi  grain  of  aconitino  yields  a  very  copious  precipitate. 

2.  yx,V(r  gi'ain  yields  a  quite  good  deposit,  which  is  readily  soluble 

to  a  clear  solution  in  potassium  hydrate. 
''^-  :7(M)(i  g'"^i'i  yields  in  a  very  little  time  a  quite  fair  precipitate. 

4.  x^(i.|,yo  grain  yields  after  a  little  time  a  quite  perceptible  deposit. 

5.  ijif.Vinr  gi"^'"  •  after  some  time  a  just  perceptible  turbidity. 

3.  Picric  Acid. 

An  alcoholic  solution  of  picric  acid  occasions  in  solutions  of  salts 
of  aconitine  a  yellow,  amorphous  precipitate,  wliich  is  insoluble  in 
ammonia. 

1.  y-J-jj-  grain  of  aconitine,  in  one  grain  of  water,  yields  a  very  copious 

precipitate. 

2.  YijVij-  grain  yields  a  quite  fair,  greenish-yellow  deposit. 

3.  g  ^(^  Q  grain  :  after  a  little  time  a  quite  perceptible  precipitate. 

4.  Iodine  in  Potassium  Iodide. 

An  aqueous  solution  of  iodine  in  potassium  iodide  throws  down 
from  solutions  of  aconitine  and  of  its  salts,  even  when  highly  diluted, 
a  reddish-brown  or  yellowish,  amorphous  precipitate,  which  is  readily 
decomposed  by  the  caustic  alkalies. 

1.  -j-OTT  gi'ain  of  aconitine  yields  a  very  copious  precipitate,  which  on 

the  addition  of  potassium  hydrate  is  changed  to  a  white  deposit. 

2.  YoVo"  grain:  a  copious,  yellowish  precipitate,  which  is  soluble  in 

the  caustic  alkalies,  but  immediately  replaced  by  a  white  deposit. 

3.  xo.^ij-j)-  grain  :  a  quite  good  precipitate. 

4.  3-g-,V(r(r  grain  yields  a  quite  distinct  deposit. 

5.  xTo.VuT  gi'ain  :  the  mixture  becomes  distinctly  turbid. 

5.  Bromine  in  Bromohydric  Acid. 

A  strong  aqueous  solution  of  bromohydric  acid  saturated  ^vith 
bromine  produces  in  solutions  of  salts  of  aconitine,  and  of  the  free 
alkaloid,  a  yellow,  flocculent  precipitate. 

1.  -j-^  grain  of  aconitine,  in  one  grain  of  water,  yields  a  copious 

precipitate. 

2.  YdVo"  gi'ain  :  a  quite  good  deposit. 


628  ACONITINE. 

3.  3-0,^-00"  grain  :  a  quite  fair  precipitate. 

4.  2T,"ooT  gi'^ii^  yields  a  distinct  cloudiness. 

Other  Reagents. —  Corrosive  sublimate  produces  in  one  grain  of 
a  1-lOOth  solution  of  salts  of  aconitine  a  quite  good,  dirty-white, 
caseous  precipitate,  which  is  readily  soluble  in  hydrochloric  acid. 
A  similar  quantity  of  a  l-500th  solution  of  the  alkaloid  fails  to 
yield  a  precipitate.  Potassium  sulphocyanide  and  tannic  acid  pro- 
duce a  perceptible  cloudiness  in  a  1-lOOth  solution  of  salts  of  the 
alkaloid.  AVith  stronger  solutions  these  reagents  produce  distinct 
precipitates.  Pliospho-molyhdic  acid  throws  down  a  precipitate  from 
solutions  of  the  alkaloid  even  when  highly  diluted. 

Platinic  chloride,  potassium  chroraates,  potassium  iodide,  and 
potassium  ferro-  and  ferri-cyanide,  fail  to  produce  a  precipitate  with 
a  1-lOOth  solution  of  the  hydrochloride  of  the  alkaloid. 

FaUacies. — None  of  the  chemical  reactions  now  described  are  in 
themselves  characteristic  of  aconitine,  they  being  common  to  many 
of  the  alkaloids  and  certain  other  organic  principles;  nor  is  there  at 
present  any  chemical  reaction  known  that  in  itself  is  peculiar  to  this 
substance.  By,  however,  the  concurrent  reaction  of  several  of  these 
reagents,  taken  in  connection  with  the  peculiar  effects  of  the  alkaloid 
upon  the  tongue,  its  nature  may  be  fully  established,  even  when 
present  only  in  very  minute  quantity.  In  fact,  the  symptoms  pro- 
duced by  this  substance  are  usually  so  peculiar  that  they  alone,  when 
fully  known,  may  enable  the  medical  jurist  to  determine  the  cause 
of  death,  even  when  the  chemical  evidence  has  entirely  failed.  A 
case  of  this  kind,  in  which  the  root  of  aconitine  had  been  criminally 
administered  and  no  trace  of  the  poison  was  discovered  in  the  body, 
is  related  by  Dr.  Geoghegan.  [Dublin  Medical  Journal,  July,  1841, 
403.) 

Physiological  Test. — Much  the  most  characteristic  test  yet  known 
for  the  recognition  of  aconitine  is  its  peculiar  physiological  action 
when  applied  to  the  tongue  or  in  the  form  of  solution  to  the  skin. 
A  drop  of  water  holding  in  solution,  in  the  form  of  a  salt,  only  the 
1-lOOOth  of  a  grain  of  the  alkaloid,  when  placed  upon  the  end  of 
the  tongue,  causes,  as  first  observed  by  Dr.  Headland,  a  very  decided 
tingling  and  numbness  of  that  organ,  which  continue  for  an  hour  or 
longer.  According  to  Dr.  Headland  {Action  of  Medicines,  448),  the 
1-1 00th  of  a  grain  dissolved  in  alcohol  and  rubbed  into  the  skin 


SKP.MJATIO.V    Fi:(».M    oltOANIC    MIXTURES.  G29 

pidiliioes  loss  of  feellnir,  lasting  for  sonic  time;  and  the  l-50lli  oi'  :i 
grain  will  kill  a  small  hinl  almost  instantly. 

Jn  an  exiK'rinieiit  by  Dr.  T.  Stevenson,  l-3000tli  grain  of  Mor- 
son'.s  crystallized  aconitine,  subcutaneously  injected,  killed  a  large 
mouse  in  eighteen  minutes.  And  our  own  exj)eriment.s  with  Du- 
quosncl's  crystallized  aconitine  indicated  it  to  be  about  equally  potent, 
1-WOOth  grain  proving  fatal  to  a  mouse,  under  violent  retching 
followed  by  convulsions,  in  thirty-two  minutes.  A  sample  of  Mor- 
son's  ordinary  aconitine  was  somewhat  less  active  than  the  crvstal- 
lizeil  alkaloid  of  Duquosnel ;  as  was  also  a  sample  of  Trommsdorff's 
aconitine,  which  latter  was  in  the  form  of  a  faintly  colored,  partially 
granular  powder. 

Separation  from  Organic  Mixtures. 

Suspecled  Solutiom  and  Contents  of  the  Stomach. — In  suspected 
poisoning  by  aconite  in  its  crude  state,  before  proceeding  to  a  chem- 
ical examination  of  the  mixture  presented  for  examination,  the 
analyst  should  carefully  examine  it  for  any  solid  portions  of  the 
plant,  which,  if  found,  may  be  identified  by  their  botanical  char- 
acters. All  parts  of  the  plant  have  a  bitter  taste',  which  is  soon 
followed  by  a  persistent  sense  of  numbness  and  tingling  in  the  lips 
and  tongue. 

Aconitine  may  be  separated  from  the  contents  of  the  stomach, 
and  like  mixtures,  in  the  same  manner  as  heretofore  described  for 
the  recovery  of  nicotine  {ante,  447),  or  by  the  method  of  Stas.  The 
alkaloid  is  more  readily  extracted  from  aqueous  mixtures  by  chloro- 
form than  by  ether,  it  being  much  more  soluble  in  the  former  than 
in  the  latter  liquid.  The  residue  obtained  on  evaporating  the 
chloroform  or  ether  extract  should  at  first  be  stirred  with  a  few 
drops  of  water  containing  a  trace  of  acetic  acid,  and  a  small  portion 
of  the  mixture  applied  to  the  end  of  the  tongue.  If  this  experiment 
indicates  the  presence  of  a  very  notable  quantity  of  the  poison,  the 
remaining  portion  of  the  mixture  may  be  dissolved  in  an  appropriate 
quantity  of  acidulated  M'ater  and  the  solution  examined  by  some  of 
the  chemical  tests.  Should,  however,  the  portion  applied  to  the 
tongue  fail  to  indicate  the  presence  of  the  alkaloid,  another  and 
larger  portion  should  be  examined  in  the  same  manner,  even  if  the 
whole  of  the  mixture  be  thus  consumed,  since  without  the  corrobora- 


630  ACONTTINE. 

tion  of  this  physiological  test,  the  chemical  tests,  at  present  known, 
would  be  of  no  avail. 

On  applying  the  method  heretofore  pointed  out  for  the  detection 
of  nicotine  to  the  examination  of  the  contents  of  the  stomach  of  a 
dog,  killed  in  fourteen  minutes  by  a  drachm  of  ordinary  tincture  of 
the  root  of  aconite,  the  presence  of  aconite  was  very  fully  established. 
From  the  Blood. — Absorbed  aconitine  may  be  recovered  from  the 
blood  by  slightly  acidulating  the  fluid  with  sulphuric  acid  and  agi- 
tating it  in  a  wide-mouthed  bottle  with  something  more  than  its  own 
volume  of  diluted  alcohol,  until  the  mixture  becomes  homogeneous. 
It  is  then  placed  in  an  evaporating-dish  and  exposed  for  some  time, 
with  frequent  stirring,  to  a  moderate  heat ;  the  cooled  mass  is  trans- 
ferred to  a  moistened  linen  strainer,  and  the  solids  retained  by  the 
strainer  well  washed  with  diluted  alcohol  and  strongly  pressed.  The 
liquid  is  now  concentrated  at  a  moderate  heat,  again  strained,  then 
evaporated  to  a  small  bulk,  filtered  through  paper,  and  evaporated 
on  a  water-bath  to  about  dryness.  The  residue  thus  obtained  is  well 
stirred  with  a  small  quantity  of  pure  water,  the  solution  filtered, 
then  rendered  alkaline,  and  thoroughly  agitated  with  about  two 
volumes  of  chloroform,  which,  after  separation  and  decantation,  is 
allowed  to  evaporate  spontaneously,  when  the  alkaloid  will  usually 
be  left  sufficiently  pure  for  testing. 

About  forty  minims  of  the  tincture  of-  aconite  root  were  admin- 
istered to  a  small  dog.  The  animal  immediately  indicated  an  uneasy 
sensation  in  the  mouth  and  throat,  and  soon  vomited  a  white  frothy 
mucus,  then  lost  the  use  of  his  legs,  made  repeated  attempts  to  vomit, 
had  spasmodic  convulsions  with  slow  breathing,  and  died  in  sixty- 
four  minutes  after  the  dose  had  been  given.  Twelve  fluid-drachms 
of  blood,  taken  immediately  from  the  animal,  were  submitted  to  the 
foregoing  method  of  analysis,  and  the  chloroform  residue  stirred  with 
two  drops  of  water  containing  the  merest  trace  of  acetic  acid.  A 
drop  of  this  mixture  placed  upon  the  tongue  gave,  in  a  little  time, 
perfectly  unequivocal  evidence  of  the  presence  of  aconitine.  The 
remaining  drop  of  the  mixture  was  diluted  with  two  drops  of  pure 
water,  and  examined  in  three  separate  portions  by  picric  acid,  auric 
chloride,  and  a  solution  of  bromine,  all  of  which  produced  precipi- 
tates very  similar  in  quantity  with  those  produced  from  a  1-1 500th 
solution  of  the  alkaloid.  The  entire  quantity  of  the  poison  recovered 
could  hardly  have  exceeded  the  l-300th  of  a  grain,  and  may  have 


ATROPINE.  631 

been  even  nuich  less  than  this,  since  it  is  ))y  no  means  certain  that 
the  precipitates  produced  hy  the  reagents  were  perfectly  pure. 

Twenlv-live  minims  of  the  ssanie  tincture  of  aconite  were  given 
to  a  hcaltliv  cat.  The  animal  was  soon  seized  with  violent  vomiting, 
lost  the  power  of  walking,  frothed  at  the  mouth  and  nose,  and  died 
under  violent  symptoms  within  thirly  minutes.  The  chloroform 
residue  obtained  from  one  ounce  of  blood  from  (his  animal,  when 
stirred  with  a  few  drops  of  acidulated  water  and  examined  by  auric 
chloride  and  a  solution  of  bromine,  gave  reactions  similar  to  those 
produced  from  a  quite  dilute  solution  of  aconitine;  yet  about  one- 
half  of  the  residue,  when  applied  to  the  tongue,  failed  to  produce 
any  decided  effect  u])on  that  organ. 

In  the  Lamson  case,  Drs.  Stevenson  and  Dupre  found  aconitine 
in  extracts  from  the  viscera,  the  vomit,  and  the  urine  of  the  victim, 
the  presence  of  the  alkaloid  l)eing  determined  by  the  general  chemical 
nature  of  the  extract,  its  effect  upon  the  tongue,  and  its  action  upon 
mice. 

The  ireneral  method  of  analysis  followed  in  this  case  was  to  re- 
peatedly  extract  the  substance  with  alcohol  slightly  acidulated  with 
tartaric  acid,  and  then  evaporate  the  filtered  alcoholic  extract  to  dry- 
ness at  35°  C.  (95°  F.).  The  residue  thus  obtained  was  exhausted 
with  tepid  water,  and  the  filtered  liquid,  while  still  acid,  repeatedly 
agitated  with  ether.  The  aqueous  liquid  was  then  rendered  alkaline 
by  sodium  carbonate,  and  extracted  with  a  mixture  of  ether  and 
chloroform ;  the  ethereal  mixture  was  evaporated  to  dryness,  and 
the  residue  examined  for  aconitine. 

Section  II. — Atropine.     Belladonna. 

History. — Atropine  is  the  active  principle,  or  alkaloid,  of  Atropa 
Belladonna,  or  Deadly  Nightshade.  It  exists  in  the  root,  leaves,  and 
berries  of  the  plant.  The  existence  of  this  principle  was  first  an- 
nounced in  1819,  by  Brandes;  but  it  was  first  obtained  in  its  pure 
state  by  Mein,  a  German  pharmaceutist,  in  1833.  Its  composition, 
according  to  the  analyses  of  Planta,  is  0,71123X03.  Atropine  is  a 
white  crystal  I  izable  solid,  and  a  most  virulent  poison. 

Preparation. — Atropine  may  be  obtained,  according  to  M.  Ra- 
bourdin,  in  the  following  manner.    The  fresh  leaves  of  the  plant  are 


632  ATROPINE. 

well  bruised  and  submitted  to  pressure  to  extract  the  juice;  this  is 
theu  heated  to  about  85°  C,  (185°  F.),  in  order  to  coagulate  the  albu- 
men, and  filtered,  after  which  it  is  rendered  alkaline  by  potassium 
hydrate,  and  thoroughly  agitated  for  a  few  miuutes  with  chloroform. 
In  about  half  an  hour,  the  latter  fluid,  holding  in  solution  the  atro- 
pine and  having  the  appearance  of  a  greenish  oil,  will  have  subsided 
to  the  bottom  of  the  mixture.  The  supernatant  liquid  is  then  de- 
canted, and  the  chloroform  solution  washed  with  successive  portions 
of  water  as  long  as  this  liquid  becomes  colored.  The  chloroform 
solution  is  then  transferred  to  a  tubulated  retort,  and  distilled  in  a 
water-bath  until  all  the  chloroform  has  passed  into  the  receiver,  when 
the  residue  is  treated  with  a  little  water  acidulated  with  sulphuric 
acid,  which  will  dissolve  the  atropine,  leaving  a  green,  resinous  matter. 
The  solution  thus  obtained  is  filtered,  the  filtrate  treated  with  slight 
excess  of  potassium  carbonate,  and  the  precipitated  atropine  collected 
on  a  filter,  washed,  and  dissolved  in  rectified  alcohol,  which  upon 
spontaneous  evaporation  will  leave  the  alkaloid  in  beautiful  groups 
of  acicular  crystals. 

In  the  absence  of  the  fresh  plant,  M.  Rabourdin  recommends 
to  employ  the  extract  of  belladonna.  Thirty  parts  of  the  extract  are 
dissolved  in  one  hundred  parts  of  water,  and  the  filtered  solution 
agitated  for  about  a  minute  with  two  parts  of  potassium  hydrate  and 
fifteen  parts  of  chloroform.  The  subsequent  steps  of  the  process  are 
the  same  as  directed  above,  except  that  the  washed  chloroform  solu- 
tion, instead  of  being  distilled,  is  allowed  to  evaporate  spontaneously. 
The  product  obtained  by  either  of  these  methods,  if  not  perfectly 
colorless,  may  be  further  purified,  as  fii^st  advised  by  Prof.  Procter, 
bv  redissolviug  it  in  water  acidulated  with  sulphuric  acid  and  extract- 
ing the  foreign  organic  matter  by  chloroform  ;  the  aqueous  solution 
is  then  rendered  alkaline,  and  the  liberated  alkaloid  extracted  with 
fresh  chloroform,  which  on  spontaneous  evaporation  will  leave  it  in 
its  pure  state.  M.  Lefort  has  advised  the  use  of  ether,  instead  of 
chloroform,  for  the  extraction  of  the  alkaloid,  the  latter  being  first 
extracted  from  the  leaves  of  the  plant  by  boiling  water  containing 
one  per  cent,  of  tartaric  acid. 

Mein,  in  his  experiments,  obtained  twenty  grains  of  atropine  from 
twelve  ounces  of  the  fresh  root  of  belladonna;  and  Luxton,  between 
five  and  six  grains  from  one  thousand  grains  of  the  fresh  leaves.  On 
an  average,  perhaps,  the  green  root  and  leaves  do  not  contain  over 


PHYSIOLOGICAL   EFFECTS.  63.'i 

nboiit  one-third  of  one  per  (rut,  of  the  alUidoid.  Accord iii<r  to  M. 
Lcfort,  the  proportion  of  iitropiiie  in  bclijidonnu  root  varies  very 
j;reatly  a<'cordin>^  to  the  aL!;e  of  the  phint,  yonng  roots  l^eing  richer 
in  the  alkaloid  tlian  the  rottts  of  plants  more  than  two  or  three  years 
oKl. 

The  ordinary  medicinal  dose  of  alrojune,  and  its  salts,  is  about 
one-liftieth  of  a  grain.  Tlie  pharmaceutical  extracts  and  tincture  of 
belladonna  are  each  subject  to  great  variation  in  strength.  The  dose 
of  the  former,  for  an  adult,  is  at  first  from  one-fourth  to  one-half  a 
grain;  that  of  the  latter,  from  fifteen  to  twenty-five  minims. 

Poisoning  by  atropine  in  its  i)ure  state  has  been  of  rather  rare 
occurrence;  but  numerous  instances  of  poisoning  by  the  berries  and 
some  of  the  preparations  of  belladonna  are  recorded.  With  few 
exceptions,  however,  these  cases  have  been  the  result  of  accident, 
most  of  them  having  been  occasioned  by  the  berries  being  eaten 
through  ignorance  of  their  properties.  The  berries  have  considerable 
resemblance  to  cherries,  and  a  sweet  but  mawkish  taste. 

Symptoms. — The  most  constant  symptoms  occasioned  by  poi- 
sonous doses  of  belladonna  are  dryness  of  the  mouth  and  throat, 
difficulty  of  deglutition,  dilatation  of  the  pupils,  impaired  vision, 
and  delirium,  succeeded  by  drowsiness  and  stupor.  The  delirium  is 
generally  of  a  pleasing  character,  but  sometimes  of  a  furious  nature. 
These  effects  are  usually  attended  with  a  sense  of  burning  and  con- 
striction of  the  throat,  impaired  articulation,  great  thirst,  giddiness, 
numbness  of  the  limbs,  a  staggering  gait,  nausea  and  sometimes 
vomiting,  spectral  illusions,  and  great  mental  excitement.  The  pulse 
becomes  quick  and  small,  and  sometimes  the  face  red  and  turgid,  and 
the  eyes  wholly  insensible  to  light.  The  secretions  are  usually  in- 
creased ;  irritation  of  the  urinary  organs  has  sometimes  occurred  ;  and 
in  some  instances  a  scarlet  eruption  has  appeared  on  the  skin.  In 
fatal  cases,  death  is  usually  preceded  by  coldness  of  the  extremities, 
a  rapid  and  intermittent  jiulse,  deep  coma,  and  sometimes,  though 
rarely,  convulsions. 

The  following  symptoms  were  observed  in  one  hundred  and  fifty 
French  soldiers,  who  had  eaten  the  berries  of  the  ])lant :  Dilatation 
and  immobility  of  the  pupil,  with  total  insensibility  of  the  eye  to 
the  presence  of  external  objects,  or  at  least  confused  vision ;  bluish 
injection  of  the  conjunctiva;  great  prominence  of  the  eye;  dryness 
of  the  lips,  tongue,  and  throat;  difficult  and  in  some  cases  impossi- 


634  ATEOPIXE. 

ble  deglutition;  nausea,  but  no  vomiting;  great  weakness,  with 
difficulty  or  impossibility  of  standing;  continual  movement  of  the 
hands  and  fingers;  lively  delirium,  accompanied  with  a  silly  laugh; 
aphonia,  or  confused  sounds  uttered  with  difficulty;  and  ineffectual 
attempts  to  empty  the  bowels.  These  effects  were  followed  by  very 
gradual  return  to  health  and  reason,  without  any  recollection  of  the 
preceding  state.     {Orfila's  Toxicologie,  1852,  ii.  478.) 

The  symptoms  produced  by  belladonna,  as  usually  developed, 
could  not  readily  be  confounded  with  those  of  any  other  substance, 
except  stramonium  and  hyoscyamus  (Pereira).  The  symptoms 
usually  manifest  themselves  within  an  hour  after  the  poison  has 
been  taken  ;  but  they  have  frequently  been  delayed  for  several 
hours,  especially  in  poisoning  by  the  berries.  Of  the  numerous 
recorded  cases  of  poisoning  by  this  substance,  comparatively  few 
proved  fatal,  and  in  these  the  time  of  death  varied  from  a  few 
hours  to  some  days.  The  effects  in  non-fatal  cases  are  frequently 
very  slow  in  disappearing,  sometimes  lasting  for  several  days  or  even 
weeks. 

A  healthy  man  ate  of  a  pie  made  with  the  berries  of  belladonna 
and  apples.  A  few  minutes  after  taking  his  dinner  he  complained 
of  feeling  drowsy ;  the  lethargy  soon  increased,  his  countenance 
changed  color,  the  ])upils  became  dilated,  and  he  experienced  a 
strange  coppery  taste  in  his  mouth.  On  going  up-stairs,  he  staggered, 
and,  upon  entering  his  room,  fell,  and  became  insensible.  He  sub- 
sequently became  delirious  and  convulsed,  and  died  the  following 
morning.  A  child  to  whom  a  })ortion  of  the  pie  had  been  given 
died  on  the  same  day.  {New  York  Jour,  of  Med.,  viii.  284.)  In 
another  case,  in  which  a  child  had  eaten  the  berries  of  the  plant, 
narcotic  symptoms  appeared  in  two  hours,  and  death  took  place  in 
nineteen  hours,  being  preceded  by  coma  and  a  temperature  of  43.3° 
C.  (110°  F.)  for  several  hours  before  the  fatal  result.  [Med.  Times, 
Nov.  1882,  94.) 

In  four  cases  in  which  some  boys  had  eaten  a  quantity  of  the 
extract  of  belladonna,  in  one  instance  as  much  as  a  drachm,  the 
following  symptoms  were  observed  in  one  of  the  cases.  When  first 
seen  by  a  physician,  the  patient  was  quite  delirious,  the  delirium 
being  of  a  fantastic  character ;  he  could  neither  hear  nor  speak 
plainly,  and  labored  under  hallucinations,  but  was  otherwise  uncon- 
scious.    The  pupils  were  widely  dilated,  and  the  eyes  had  a  staring 


PHYSIOLOGICAL    EFFECTS.  635 

look.  At  first  he  complained  of  some  i)aiii  in  tlie  throat  and  of  his 
imperfect  slight,  ohjeets  ap|)earing  white  to  him.  The  pulse  was  very 
feehle,  and  ahnost  countless;  and  there  was  threat  difficulty  of  swal- 
lowing. Under  active  treatment,  including  the  use  of  an  emetic, 
the  delirium,  having  lasted  eighteen  hours,  gradually  passed  away; 
but  it  was  not  until  the  lapse  of  forty  hours  that  he  was  perfectly 
rational.  Much  the  same  symptoms  were  present  in  the  three  other 
cases.     All  the  patients  finally  recovered.     {Lancet,  1860,  i.  133.) 

Dr.  Ilibbert  Taylor  reports  a  case  {British  Med.  Jour.,  Nov. 
1869,  555)  in  which  a  youth,  aged  sixteen  years,  swallowed  by  mis- 
take about  a  drachm  of  the  extract,  and  died  from  its  effects  three 
hours  and  three-quarters  thereafter.  In  this  instance,  violent  symp- 
toms suddenly  manifested  themselves  about  an  hour  after  the  extract 
had  been  taken.  About  an  hour  before  death  the  patient  became 
comatose,  and  so  continued  until  he  died. 

The  following  instance  of  recovery  is  related  by  Dr.  H.  M.  Gray. 
{New  York  Jour,  of  Med.,  Sept.  1845,  182.)  A  child,  between  two 
and  three  years  of  age,  swallowed  from  eight  to  twelve  grains  of  the 
extract  of  belladonna.  Something-  over  half  an  hour  after  taking; 
the  poison,  the  expression  of  the  patient  was  that  of  terror ;  the 
pupils  were  widely  dilated  and  immovable,  the  conjanctiva  highly 
injected,  and  the  whole  eye  prominent  and  very  brilliant.  The  face, 
upper  extremities,  and  trunk  of  the  body  exhibited  a  diffuse  scarlet 
eflBorescence  studded  with  innumerable  papillae,  very  closely  resem- 
bling the  rash  of  scai'latina.  The  skin  was  hot  and  dry;  the  pulse 
much  increased  in  force  and  frequency ;  the  respiration  anxious,  and 
attended  with  the  stridulous  sound  of  croup.  There  was  also  a 
constant  but  unsuccessful  effort  at  deglutition,  with  spasmodic  action 
of  the  muscles  of  the  throat  and  pharynx ;  and  paroxysms  of  violent 
motion  and  rapid  automatic  movements,  attended  with  convulsive 
laughter.  Under  the  action  of  an  emetic  the  alarming  symptoms 
passed  off  in  about  three  hours,  and  the  child  soon  recovered,  with 
the  exception  of  a  moderate  diarrhoea  and  a  slight  enlargement  of 
the  pupil.  Dr.  Stevenson  reports  a  case  {Guy's  Hosp.  Rep.,  xiv. 
267)  in  which  a  child,  less  than  three  years  of  age,  recovered  after 
having  taken  five  grains  of  the  extract. 

The  external  application  of  belladonna,  and  its  administration  in 
the  form  of  an  enema,  have  in  several  instances  given  rise  to  serious 
and  even  fatal  results.     A  case  is  related  in  which  an  injection  of  a 


686  ATEOPINE. 

decoction  of  the  root  caused  the  death  of  au  adult  in  five  hours  ;  and 
another,  in  which  only  two  grains  of  the  extract,  administered  in 
the  same  manner,  gave  rise  to  alarming  symptoms.  Dr.  Lyman 
relates  an  instance  in  which  the  application  of  a  small  belladonna 
plaster  to  the  chest  of  a  nervous  woman  produced  all  the  usual 
symptoms  of  poisoning  by  that  substance,  from  which  the  patient 
did  not  entirely  recover  until  after  four  or  five  days.  Two  cases  of 
this  kind,  in  which  a  lotion  of  belladonna  had  been  applied,  are 
mentioned  in  the  Chemical  News  (London,  Nov.  1866,  216). 

In  a  case  reported  by  Dr.  Smith  [Boston  Med.  and  Surg,  Jour., 
Dec.  1879,  895),  an  application  of  belladonna  ointment  to  the  neck 
of  the  womb  of  a  woman  in  labor  was  followed  in  less  than  fifteen 
minutes  by  dizziness,  succeeded  in  quick  succession  by  great  thirst, 
dryness  and  burning  of  the  mouth  and  fauces,  nausea  and  ineffectual 
attempts  to  vomit,  spasmodic  movements  of  the  arms,  and  striking 
at  imaginary  objects.  There  were  short  intervals  of  repose,  then 
sudden  convulsive  movements ;  the  pulse  became  feeble,  the  extremi- 
ties cold,  and  the  pupils  widely  dilated.  Under  the  subcutaneous 
injection  of  a  third  of  a  grain  of  morphine  the  convulsive  move- 
ments soon  subsided ;  but  the  thirst  and  dryness  of  the  throat  re- 
mained for  ten  or  twelve  hours.  Labor-pains  did  not  again  appear 
for  ten  days,  when  the  woman  was  safely  delivered. 

Atropine. — The  symptoms  produced  by  atropine  in  its  pure  state 
are  the  same  in  kind  as  those  occasioned  by  belladonna,  but  they  are 
usually  much  more  prompt  in  appearing.  In  a  case  related  by  Dr. 
Schmid,  a  stout,  healthy  man  swallowed  from  one-sixth  to  one-fourth 
of  a  grain  of  the  alkaloid  in  solution.  An  hour  afterward,  the  patient 
was  in  a  state  of  fearful  excitement ;  the  tongue  was  swollen  and  pro- 
jected between  the  teeth,  and  he  incessantly  moved  it  and  his  lips  in 
a  stammering  manner,  but  without  emitting  a  single  intelligible  word. 
The  eyes  were  staring;  the  head  hot,  and  the  countenance  livid;  the 
pupils  dilated  to  their  utmost,  and  insensible  to  light ;  the  pulse  was 
rapid,  full,  and  strong,  and  there  was  a  constant  desire,  but  without 
the  power,  to  make  water.  During  the  following  hour  the  excitement 
continually  increased,  when  the  subcutaneous  injection  of  one-fifth  of 
a  grain  of  morphine  acetate  into  the  right  temple  was  soon  succeeded 
by  a  state  of  calm.  After  two  hours  more,  the  excitement  had  again 
attained  almost  its  former  height,  but  it  was  again  subdued  by  a  repe- 
tition of  the  morphine  injection.    The  patient  now  gradually  recovered, 


PHYSIOLOGICAL   EFFECTS.  637 

the  only  symptoms  remaining  about  twenty-four  hours  after  the  oc- 
currence being  extreme  weakness,  dryness  of  the  tliroat,  slight  twitch- 
ings  of  the  limbs,  and  a  dilated  state  of  the  pupils.  [Amer.  Jour.  Med. 
/&/.,  July,  18(J6,  269.) 

Dr.  S.  W.  Gross  reports  a  case  [Amer.  Jour.  Med.  ScL,  Oct.  18G9, 
401)  in  which  a  healthy  woman,  aged  forty-three  years,  througii  the 
mistake  of  a  druggist,  took  some  pills  containing  {/tree  grains  of 
atrojiine,  and  died  from  the  effects  of  the  poison  in  about  fifteen  hours 
after  taking  the  dose.  The  symptoms  in  this  case  began  in  about 
fifteen  minutes  after  the  pills  had  been  taken,  there  being  at  first  vio- 
lent agitation,  soon  followed  by  pleasant  delirium,  in  which  the  patient 
picked  at  her  clothes,  tried  to  get  out  of  bed,  and  imagined  she  was 
sewing,  or  nursing  her  child,  or  engaged  in  shopping  with  her  sister. 

Dr.  Andrew,  of  Edinburgh,  relates  an  instance  in  which  two-thirds 
of  a  grain,  taken  in  mistake  by  a  female,  produced  most  violent  symp- 
toms, from  which  the  patient  did  not  entirely  recover  for  more  than 
a  week.  (Wharton  and  Stills,  Med.  Jur.,  639.)  And  in  a  more 
recent  case,  a  similar  quantity  of  the  sulphate  of  the  alkaloid,  taken 
by  a  lady,  caused  most  alarming  symptoms  during  a  period  of  eighteen 
hours,  although  the  contents  of  the  stomach  had  been  early  evacuated 
by  means  of  the  stomach-pump.  {Amer.  Jour.  Pharm.,  July,  1871, 
324.)  An  instance  is  mentioned  in  which  a  solution  of  oidy  one- 
twelfth  of  a  grain  of  atropine  taken  in  mistake  by  a  physician  caused 
his  death  in  about  thirty  hours.  [Gaillard's  Med.  Jour.,  May,  1880, 
583.) 

On  the  other  hand,  Dr.  Roux  has  reported  an  instance  in  which 
a  lady,  in  a  fit  of  despair,  swallowed  a  solution  containing  nearly 
two  grains  of  atropine,  and  entirely  recovered,  not,  however,  with- 
out suffering  the  most  severe  symptoms.  The  treatment  employed 
in  this  case  consisted  of  emetics,  followed  by  a  strong  decoction  of 
coffee  and  M.  Bouchardat's  solution  of  iodine  in  potassium  iodide. 

The  employment  of  atropine  in  the  form  of  subcidaneous  injec- 
tion has  in  repeated  instances  been  followed  by  very  serious  and 
even  fatal  results,  even  when  injected  in  very  minute  quantity.  Dr. 
Eulenberg  relates  an  instance  in  which  he  employed  in  this  manner, 
in  the  case  of  a  ladv  affected  with  facial  neuralo:ia,  l-48th  of  a  frrain 
of  the  alkaloid,  and  alarming  symptoms  of  poisoning  soon  appeared. 
The  patient  threw  herself  about  the  bed  entirely  unconscious,  and 
from  time  to  time  broke  out  in  furious  delirium;  the  limbs,  and  also 


633  ATROPINE. 

the  head,  were  shaken  with  convulsive  jerkiugs.  The  pupils  were 
moderately  dilated,  the  pulse  small,  and  somewhat  increased  in  fre- 
quencv.  An  immediate  injection  of  one-third  of  a  grain  of  morphine 
into  the  temporal  region,  in  close  proximity  to  the  former  place  of 
injection,  was  followed  within  about  three  minutes  by  a  cessation  of 
the  twitchings,  and  in  ten  minutes  the  patient  fell  into  a  hea%y,  peace- 
ful sleep,  from  which  she  awoke  in  eight  hours  without  any  symptom 
of  the  poison  being  present.  [Amer.  Jour.  Med.  Sci.,  April,  1866, 
434.)  In  another  case,  related  by  Dr.  Lorent,  less  than  the  1-lOOth 
of  a  grain  of  the  alkaloid,  employed  in  this  manner,  produced  very 
alarming  results.  Dr.  Arnold  mentions  an  instance  in  which  death 
resulted  in  five  minutes  from  the  one-thirtieth  of  a  grain  of  atropine 
given  hypodermically.  {Baltiraore  Med.  Jour.,  March,  1871,  169.) 
On  the  other  hand,  Dr.  T.  B.  Jewett  relates  a  case  in  which  recovery 
took  place  after  the  subcutaneous  injection  of  a  solution  of  one  grain 
of  atropine,  three  grains  of  morphine  having  been  administered 
hypodermically  soon  after  the  atropine  had  been  injected.  [Proc. 
Connecticut  Med.  Soc,  1879,  82.) 

The  external  application  of  atropine  may  speedily  produce  death. 
In  an  instance  reported  by  Dr.  Ploss,  of  Leipsic,  an  ointment  com- 
posed of  fifteen  parts  of  atropine  sulphate  to  seven  hundred  parts  of 
lard,  applied  as  a  dressing  to  a  blistered  surface  on  the  neck  of  a  man, 
caused  death,  under  the  most  violent  symptoms  of  belladonna  poison- 
ing, within  two  hours  after  the  application  had  been  made.  [Amer. 
Jour.  Med.  Sci.,  April,  1865,  541.)  A  few  drops  of  an  aqueous  so- 
lution containing  two-thirds  of  a  grain  of  the  alkaloid  to  the  ounce 
of  fluid,  applied  to  the  eye  of  a  man  affected  with  cataract,  produced 
violent  constitutional  effects,  with  constant  hallucinations,  and  inabil- 
ity to  pass  urine;  the  violent  delirium  continued  during  the  ensuing 
night,  and  it  was  some  days  before  the  patient  entirely  recovered. 

Teeatment. — This  consists,  in  case  the  poison  has  been  swal- 
lowed, in  the  speedy  administration  of  an  emetic  or  the  employment 
of  the  stomach-pump.  Of  the  various  chemical  antidotes  that  have 
been  proposed  may  bo  mentioned  tannic  acid,  a  solution  of  iodine 
in  potassium  iodide,  hydrate  of  magnesia,  and  animal  charcoal.  If 
either  of  these  substances  be  employed,  it  should  only  be  in  connec- 
tion with  emetics  or  the  use  of  the  stomach-pump. 

As  a  physiological  antidote,  morphine,  administered  either  by  the 
mouth  or  by  subcutaneous  injection,  has  been  found  very  beneficial, 


PA'nioLoCilCAl,     KFFKCTS.  039 

as  ill  sonic  of  tlie  instances  already  cited.  In  a  case  of  recovery  men- 
tioned by  Dr.  J.  B.  Cox,  in  which  one  grain  of  atroiiine  liad  been 
taken,  it  is  said  that  from  sixteen  to  eighteen  grains  of  morphine 
were  injected  hypodermically  without  there  being  at  any  time  symp- 
toms of  narcotism  from  the  use  of  the  mor|)hine.  [Med.  Times,  Feb. 
188-1,  377.) 

rUocarpinc,  employed  subcutaneously,  has  also  been  strongly 
advised  in  atropine  poisoning.  Dr.  Purjesz  relates  a  case  in  which 
about  two  grains  and  a  half  of  atropine  had  been  taken,  and  under 
the  use  of  repeated  injections  of  a  salt  of  pilocarpine,  using  in  all 
about  6.4  grains  of  the  salt,  the  toxic  symptoms  gradually  subsided, 
and  at  the  end  of  three  hours  after  taking  the  atropine  the  patient 
had  quite  recovered,  even  the  dilatation  of  the  pupils  having  passed 
off. 

Post-mortem  Appearances. — These,  as  in  death  from  most 
of  the  vegetable  poisons,  are  subject  to  considerable  variation.  The 
more  constant  appearances  are  a  dilated  state  of  the  pupils,  more  or 
less  redness  of  the  raucous  membrane  of  the  stomach  and  small  intes- 
tines, fulness  of  the  cerebral  vessels,  and  congestion  of  the  lungs. 
The  blood  is  usually  dark-colored  and  liquid.  Instances  are  related, 
however,  in  which  this  poison  produced  death  without  leaving  any 
notable  morbid  change  in  the  body. 

In  the  case  reported  by  Dr.  H.  Taylor,  in  which  a  drachm  of  the 
extract  of  belladonna  had  been  taken,  eighteen  hours  after  death,  the 
pupils  were  found  greatly  dilated.  The  lungs  were  much  engorged  ; 
and  the  pleural  cavities  contained  a  little  dark  blood.  The  heart 
was  empty,  except  the  right  auricle,  which  contained  about  six 
drachms  of  dark,  semi-coagulated  blood.  The  stomach  was  fragile 
and  softened  in  texture.  AH  the  other  abdominal  organs  appeared 
healthy. 

In  Dr.  Gross's  case,  in  which  three  grains  of  atropine  had  been 
taken  and  proved  fatal  in  about  fifteen  hours,  thirty-eight  hours 
after  death  the  pupils  were  somewhat  dilated,  and  the  face  was  livid. 
The  vessels  of  the  pia  mater  Avere  turgid  with  blood,  and  there  was 
great  subarachnoid  effusion ;  the  brain-tissue  was  greatly  softened. 
The  lungs  were  congested  ;  the  heart  was  very  soft,  and  its  cavities 
contained  fluid  blood.  The  intestines  were  pale,  but  the  stomach 
presented  suggillations  at  its  cardiac  extremity;  the  kidneys  were 
congested ;  and  the  bladder  was  empty. 


640  ATROPrN'E. 

Chemical  Peopeeties. 

Ix  THE  Solid  State. — Atropine,  in  its  pure  state,  is  a  white^ 
odorless  solid,  Avhich  crystallizes  in  the  form  of  transparent  prisms, 
usually  aggregated  into  beautiful  tufts  or  stellated  groups.  It  has  a 
bitter,  acrid  taste,  ^'hen  heated  in  a  tube,  it  readily  fuses  to  a  color- 
less, transparent  liquid,  which  ascends  the  sides  of  the  tube ;  upon 
cooling,  the  liquid  becomes  a  clear  gummy  mass,  and  ultimately  con- 
cretes to  a  vitreous  solid.  ^Yhen  gradually  heated  on  porcelain,  it 
fuses  and  is  slowly  dissipated,  giving  rise  to  dense  white  fumes.  Ac- 
cording to  Planta,  the  fusing  point  of  atropine  is  90°  C.  (194°  F.), 
and  at  140°  (284°  F.)  it  is  volatilized,  partially  unchanged,  the  greater 
part  undergoing  decomposition.  When  rapidly  heated,  it  melts,  puffs 
up,  then  evolves  dense  white  fumes,  and  takes  fire,  burning  with  a 
bright  flame,  and  leaving  a  shining  black  cinder,  which  may  be 
entirely  consumed.  Heated  in  contact  with  a  fixed  caustic  alkali, 
it  readily  undergoes  decomposition,  with  the  evolution  of  ammonia. 

Atropine  has  strongly  basic  properties,  and  completely  neutralizes 
even  the  most  powerful  acids,  forming  salts,  several  of  which  are 
readily  crystallizable.  Concentrated  nitriG  acid  dissolves  the  pure 
alkaloid  without  change  of  color,  even  upon  the  application  of  heat : 
the  subsequent  addition  of  stannous  chloride  produces  no  visible 
change.  So,  also,  concentrated  sulphuric  acid  dissolves  it  to  a  color- 
less solution,  which  is  unchanged  by  a  crystal  of  potassium  nitrate; 
on  the  addition  of  a  crystal  of  potassium  bichromate,  the  acid  solu- 
tion slowly  acquires  a  green  color,  due  to  the  formation  of  chromium 
sesquioxide. 

Solubility. — A  sample  of  atropine  examined  by  Planta  was  solu- 
ble in  299  parts  of  water  at  the  ordinary  temperature;  but  a  single 
experiment  in  our  own  hands  indicated  that  the  alkaloid  requires 
414  parts  of  that  liquid  for  solution,  even  after  several  hours'  diges- 
tion. It  is  readily  soluble  in  nearly  every  proportion  in  alcohol  and 
in  chloroform,  and  is  freely  soluble  in  absolute  eihe:)\  Upon  sponta- 
neous evaporation,  it  separates  from  either  of  these  liquids  in  the 
crystalline  form.  A  saturated  aqueous  solution  of  the  alkaloid  has 
a  well-marked  alkaline  reaction.  Most  of  the  salts  of  atropine  are 
freely  soluble  in  water  and  in  alcohol ;  but  they  are  almost  wholly 
insoluble  in  ether  and  chloroform ;  at  least  this  is  the  case  with  the 
sulphate  and  hvdrochloride. 


BROMINE    IN    BROMOHYDRIC    ACID   TEST.  G41 

Op  Solutions  op  Atropine. — The  following  result's,  in  regard 
to  the  beliiivior  of  solutions  of  atroi)ine,  are  based  upon  the  exam- 
ination of  two  apj)arcntly  perfectly  pure  specimens  of  the  alUaloid, 
pre[)arecl  by  (litlc'rent  well-known  European  manufacturers,  one  of 
the  samples  being  employed  in  the  form  of  sulphate,  and  the  other 
as  hydrochloride.  The  fractions  em|)l()yed  indicate  the  fractional 
part  of  a  grain  of  the  pure  alkaloid  i)resent  in  one  grain  of  water; 
and  the  results,  unless  otherwise  indicated,  refer  to  the  behavior  of 
one  grain  of  the  solution. 

1.   Tlie  Caustic  Alkalies. 

The  fixed  caustic  alkalies  throw  down  from  concentrated  aqueous 
solutions  of  salts  of  atropine  a  white,  amorphous  precipitate  of  the 
pure  alkaloid,  which  is  readily  soluble  in  free  acids,  and  also  in  large 
excess  of  the  precipitant.  After  a  time,  especially  if  the  mixture 
lias  been  stirred,  the  precipitate  assumes  the  crystalline  form.  The 
presence  of  foreign  organic  matter  readily  prevents  the  formation  of 
crystals. 

One  grain  of  a  1-lOOth  solution  of  the  alkaloid  yields  a  quite 
copious  precipitate,  which  on  being  stirred  with  a  glass  rod  becomes 
in  a  little  time  a  mass  of  crystals,  of  the  forms  illustrated  in  Plate 
XII.,  fig.  4.  Solutions  but  little  more  dilute  than  this  fail  to  yield 
a  precipitate. 

Ammonia  produces  in  solutions  of  salts  of  the  alkaloid  the  same 
precipitate  as  occasioned  by  the  fixed  caustic  alkalies ;  but  the  deposit 
is  much  more  readily  soluble  in  excess  of  the  preci})itant. 

Potassium  carbonate  produces  in  a  1-lOOth  solution  of  the  alka- 
loid a  distinct  turbidity  ;  but  the  carbonates  of  sodium  and  ammonium 
fail  to  produce  in  a  similar  solution  any  visible  reaction. 

2.  Bromine  in  Bromohydric  Acid. 

An  aqueous  solution  of  bromohydric  acid  saturated  with  free 
bromine  produces  in  solution  of  salts  of  atropine  and  of  the  free  al- 
kaloid, even  when  highly  diluted,  a  yellow,  amorphous  precipitate, 
which  in  a  little  time  becomes  crystalline.  The  precipitate  from 
somewhat  strong  solutions  of  the  alkaloid  after  a  time  disappears; 
but  it  is  immediately  reproduced  upon  further  addition  of  the  re- 
agent. The  precipitate  is  insoluble  in  acetic  acid,  and  only  very 
sparingly  soluble  in  large  excess  of  hydrochloric,  nitric,  and  sulphuric 

41  ' 


642  ATROPINE. 

acids,  and  in  the  fixed  caustic  alkalies :  it  is  even  produced  from 
solutions  of  the  alkaloid  in  concentrated  sulphuric  acid. 

1.  -j-^  grain  of  atropine,  in  one  grain  of  water,  yields  a  very  copious, 

bright  yellow,  amorphous  precipitate,  which  very  soon,  begin- 
ning along  the  margin,  becomes  a  mass  of  crystals,  Plate  XII., 
fig.  5.  After  several  minutes  most  of  the  crystals  dissolve,  but 
they  may  be  reproduced,  even  several  times,  by  further  addition 
of  the  reagent. 

2.  5oVo  grain  yields  a  copious,  yellow  deposit,  wdiich  soon  furnishes 

crystals  having  the  forms  illustrated  above. 

3.  YTT.Voo"  g^^'"  •  a  quite  good,  yellowish  precipitate,  which  in  a  few 

moments  becomes  granular  and  crystalline,  and  presents  the 
appearance  figured  in  Plate  XII.,  fig.  6. 

4.  9-5-,Viro  grai"  •  i^  a  very  little  time  a  quite  satisfactory  deposit  of 

short  crystalline  needles  and  granules. 

5.  -g-o-.^-oir  grain  :  after  some  minutes  a  few  granules  appear,  but  the 

result  is  not  satisfactory. 
The  production  of  the  above  crystals  is  quite  characteristic  of 
this  alkaloid.  Although  the  reagent  produces  yellow  precipitates 
with  most,  if  not  all,  of  the  other  alkaloids,  and  with  certain  other 
organic  substances,  yet  all  these  deposits,  with  the  exception  of 
that  from  opianyl,  unlike  the  atropine  precipitate,  remain  amor- 
phous. The  crystallized  atropine  deposit  is  readily  distinguished 
from  the  opianyl  compound  by  its  form.  It  may  here  be  remarked 
that  the  reagent  produces  a  similar  crystalline  precipitate  with 
daturine,  and  also  with  hy oscy amine ;  but,  as  we  shall  see  hereafter, 
there  are  strong  reasons  for  believing  these  alkaloids  to  be  identical 
with  atropine.  We  have  found  the  bromine  precipitate  to  become 
crystalline  in  the  presence  of  even  comparatively  large  quantities  of 
foreign  organic  matter.  In  the  absence  of  a  solution  of  bromohy- 
dric  acid,  an  alcoholic  solution  of  bromine  may  be  employed  as  the 
reagent. 

3.  Picric  Acid. 

An  alcoholic  solution  of  picric  acid  occasions  in  somewhat  strong 
solutions  of  salts  of  atropine  a  yellow,  amorphous  precipitate,  which 
is  readily  soluble  in  acids,  even  in  acetic  acid.  After  a  time  the 
precipitate  becomes  more  or  less  crystalline. 

1.  jYU  grail  of  atropine  yields  a  copious,  light  yellow  deposit.     If 
the  mixture  be  stirred  with  a  glass  rod,  it  soon  yields  streaks  of 


IODINE  TEST.  G43 

granules  along  the  jxith  of  tiic  rotl,  and  in  a  little  time  the 
deposit  becomes  entirely  crystalline,  the  crystals  being  princi- 
])ally  in  the  form  of  transparent  plates,  and  these  more  or  less 
aggregated  into  very  beautiful  groups,  Plate  XIII.,  fig.  1. 

2.  Y^(i^  grain  :  within  a  few  moments  a  slight,  greenish-yellow  pre- 

cipitate appears,  and  in  a  little  time  there  is  a  quite  good  deposit. 
If  the  mixture  be  stirred,  it  soon  yields  a  fine  crystalline  deposit. 

3.  s^Vo"  ^'■'^'•1  •    upon  stirring  the   mixture,  it  yields  after  a  little 

time  caseous  streaks  over  the  bottom  of  the  watch-glass  con- 
taining the  mixture;  but  the  reaction  is  not  very  satisfactory. 
This  reagent  also  produces  crystalline  precipitates  with  various 
other  substances,  but  the  forms  illustrated  above  are  quite  peculiar 
to  atropine. 

4.  Aiiric  Chloride. 

This  reagent  produces  iu  solutions  of  salts  of  atropine,  when  not 
too  dilute,  a  light  yellow,  amorphous  precipitate  of  atropine  chloro- 
aurafe,  Ci7H23N03,HCl,AuCl3,  which  after  a  time  becomes  converted 
into  crystals.  The  precipitate  is  insoluble  in  potassium  hydrate,  and 
but  sparingly  soluble  in  acetic  and  hydrochloric  acids. 

1.  YDT  gi'^in  of  atropine  yields  a  copious  precipitate,  which  soon 

becomes  a  mass  of  crystals  having  the  peculiar  forms  shown  in 
Plate  XIII.,  fig.  2.  " 

2.  ytjVo"  grain  yields  a  good  deposit,  which  soon,  especially  if  the 

mixture  be  stirred,  assumes  the  crystalline  form. 

3.  g  J(j  „  grain  yields  no  indication,  even  after  the  mixture  has  stood 

some  time. 
The   crystalline  form  of  the  double  atropine  salt,    as  figured 
above,  readily  distinguishes  it  from  other  substances.    The  formation 
of  these  crystals,  however,  is  readily  prevented  by  the  presence  of 
foreign  organic  matter. 

5.  Iodine  in  Potassium  Iodide. 

A  solution  of  iodine  in  potassium  iodide  throws  down  from  solu- 
tions of  salts  of  atropine,  and  of  the  free  alkaloid,  a  reddish-brown, 
amorphous  precipitate,  which  is  insoluble  in  acetic  acid,  and  only 
sparingly  soluble  in  potassium  hydrate. 
1.  Yoo"  grain  of  atropine  yields  a  very  copious  precipitate,  which 

dissolves  to  a  clear  solution  in  about  three  drops  of  a  saturated 

solution  of  potassium  hydrate. 


64:4  ATROPINE. 

2.  YoVcT  gi'ain  :  a  quite  copious  precipitate. 

3.  xo",Tjro"  gi'^iii  yields  a  very  good  deposit. 

4.  5-0-,^-oT  g'^'^iii  yields  at  first  a  yellowish  turbidity,  and  after  a  little 

time  a  distinct,  reddish-brown  precipitate. 

5.  YoifhrTo  g""^!'^  yields  a  very  distinct  turbidity. 

The  reaction  of  this  reagent  is  common  to  a  laro-e  class  of  sub- 
stances. 

Other  Reagents. — Dr.  D.  Vitali  has  lately  shown  (1880)  that  if 
atropine  or  any  of  its  salts  in  the  solid  state,  placed  in  a  porcelain 
capsule,  be  heated  with  a  few  drops  of  nitric  acid,  and  then  the 
liquid  evaporated  at  a  moderate  temperature,  the  cooled  colorless 
residue  on  being  touched  with  a  drop  of  a  concentrated  cdcoholiG 
solution  of  potassium  hydrate  will  assume  a  splendid  violet  or  purple 
color,  even  if  only  a  minute  quantity  of  the  alkaloid  be  present. 
After  a  little  time  this  color  disappears;  but  it  maybe  reproduced 
upon  the  further  addition  of  the  alcoholic  solution  of  the  caustic 
alkali. 

We  find  that  under  this  test  1-1 000th  grain  of  atropine  will 
yield  a  fine  purple  coloration,  which  may  be  reproduced  on  adding 
a  second  drop  of  the  alkaline  alcoholic  solution.  And  the  l-25,000th 
of  a  grain  yields  a  perfectly  satisfactory  purple  coloration.  A  marked 
purple  coloration  may  be  obtained  from  even  the  l-50,000th  of  a 
grain  of  the  alkaloid,  especially  if  the  alkaline  alcoholic  solution  be 
added  to  the  nitric  acid  residue  while  still  warm. 

The  reaction  of  this  test  is  common,  we  find,  to  atropine,  datu- 
riue,  hyoscyamine,  and  duboisine.  Of  some  sixty  other  alkaloids 
examined  under  this  test  by  Dr.  D.  Vitali,  he  found  none  to  give 
the  same  reactions  as  atropine  and  daturine. 

According  to  Dr.  A.  W.  Gerrard  [Pharm.  Jour,  and  Trans., 
March,  1884,  718),  if  a  little  atropine  in  a  test-tube  be  treated  with 
a  small  volume  of  a  5  per  cent,  solution  of  mercuric  chloride  in  50 
per  cent,  alcohol,  and  the  mixture  gently  warmed,  a  brick-red  pre- 
cipitate will  be  produced.  The  precipitate  has,  according  to  Dr. 
Gerrard,  the  composition  Cx7H23N03,HCl,2HgCl2,  and  may  be  ob- 
tained in  the  crystalline  state.  The  precipitate,  however,  does  not 
appear  in  dilute  solutions  of  the  alkaloid.  Dr.  Gerrard  found  this 
reaction  to  be  also  common  to  daturine,  hyoscyamine,  duboisine,  and 


8KPARATION    FROM   ORGANIC    MIXTURES.  G45 

li()m;i(roi)Iiu' ;  Imt  of  a  ntiiiihor  of  otlier  alkaloids  examined  lujne 
gave  a  red  precipitate. 

Tannic  acid  produces  in  solutions  of  salts  of  atroj)ino  a  dirty- 
white,  anior|)lioiis  precipitate,  wliicli  is  readily  solnhle  in  tiie  canstic 
alkalies  and  in  free  acids.  One  grain  of  a  1-lOOth  solntion  of  the 
alkaloid  yields  a  copions  dejjosit ;  and  a  similar  quantity  of  a 
1-lOOOth  solution  a  <|uite  distinct  reaction.  Phdinic  chloiide  and 
jjalladic  chloride  throw  down  from  concentrated  solutions  of  salts  of 
the  alkaloid  dirty-brown,  amorphous  precipitates.  Strong  solutions 
of  salts  of  atropine,  when  treated  with  a  stream  of  chlorine  gas, 
become  slightly  turbid,  and  yield  on  the  subsequent  addition  of 
ammonia  a  white  precipitate. 

Potassium  iodide,  potassium  sulphocyanide,  potassium  chromates, 
mercuric  chloride,  mercurous  nitrate,  potassium  ferro-  and  ferri- 
cyanide,  and  gallic  acid  fail  to  precipitate  even  concentrated  solu- 
tions of  salts  of  atropine. 

Physiological  Test. — The  property  possessed  by  atropine  of  di- 
lating the  pupil  of  the  eye  has  been  proposed  as  a  means  of  detecting 
its  presence.  Dr.  Headland  states  [Actioji  of  Medicine,  294)  that 
the  l-3000th  of  a  grain  of  the  alkaloid  dropped,  in  the  form  of 
solution,  into  the  eye  of  an  adult  will  answer  this  purpose.  It  must 
be  borne  in  mind,  however,  that  this  property  is  also  possessed  by 
daturine,  hyoscyamine,  duboisine,  and  certain  other  alkaloids. 

Separatiox  from  Organic  Mixtures. 

Suspected  Solutions  and  Contents  of  the  Stomach. — These  should 
first  be  carefully  examined  for  the  presence  of  any  solid  portions  of 
the  plant  or  the  seeds,  which,  if  found,  may  be  identified  by  their 
physical  and  botanical  characters.  On  account  of  the  indigestible 
nature  of  the  seeds  and  berries,  they  may  remain  in  the  alimentary 
canal  for  some  days  without  undergoing  any  change.  Dr.  Christison 
cites  several  instances  {op.  cit.,  644)  in  which  the  seeds  and  frag- 
ments of  the  fruit  were  discharged  from  the  bowels  and  bv  vomitingr 
even  several  days  after  they  had  been  taken. 

Atropine  is  separated  with  considerable  difficulty  from  complex 
organic  mixtures,  especially  when  it  exists  in  the  form  of  portions  of 
the  plant.  The  suspected  mixture,  after  comminution  of  any  solids 
present,  and  dilution  if  necessary,  is  treated  with  about  an  equal 
volume  of  strong  alcohol,  slightly  acidulated  with  sulphuric  acid, 


646  ATROPINE. 

and  exposed  for  about  half  an  hour  to  a  gentle  heat;  when  cool,  the 
liquid  portion  is  strained  through  muslin,  the  residue  washed  with 
alcohol,  and  the  strained  liquid  and  washings  concentrated  to  a  small 
bulk,  at  a  moderate  temperature,  on  a  water-bath.  If  during  the 
evaporation  much  insoluble  matter  separates,  it  is  removed  by  a 
strainer.  The  cooled  concentrated  liquid  is  passed  through  a  moist- 
ened filter,  then  washed  by  agitating  it  with  about  twice  its  volume 
of  pure  ether,  which,  after  repose,  is  carefully  decanted  and  reserved 
for  future  examination,  if  necessary ;  the  aqueous  solution  may  again 
be  washed  with  a  fresh  portion  of  ether,  and  this  removed  as  before. 
The  aqueous  liquid  is  now  rendered  slightly  alkaline  by  potassium 
hydrate  or  carbonate,  and  thoroughly  agitated  with  about  twice  its 
volume  of  pure  cldoroform,  which  will  dissolve  the  liberated  alkaloid, 
if  present ;  after  the  liquids  have  completely  separated,  the  chloro- 
form is  carefully  removed  to  a  glass  capsule  and  allowed  to  evaporate 
spontaneously. 

The  residue  thus  obtained  is  stirred  with  a  little  water  contain- 
ing a  trace  of  sulphuric  acid,  and  the  solution,  after  filtration  if 
necessary,  examined  by  some  of  the  liquid  tests  for  atropine.  As 
the  bromine  test  is  one  of  the  most  characteristic  yet  known  for  the 
identification  of  the  alkaloid,  it  should  first  be  applied  to  a  single 
drop  of  the  solution.  Another  drop  of  the  solution  may  be  evap- 
orated to  dryness  and  the  residue  examined  by  Vitali's  test.  If  the 
bromine  reagent  should  fail  to  produce  a  crystalline  precipitate,  it  is 
quite-certain  that  neither  of  the  other  liquid  tests  would  produce 
crystals,  without  which  the  results  are  common  to  a  large  class  of 
organic  substances.  It  must  not,  however,  be  expected  that  the  bro- 
mine reagent  will  always  produce  a  crystalline  deposit  containing  all 
the  forms  obtained  from  a  perfectly  pure  solution  of  atropine:  most 
frequently,  under  the  present  conditions,  the  precipitate  consists  of 
short,  opaque,  irregular  needles  and  granules,  but  these  are  charac- 
teristic of  the  alkaloid. 

In  case  the  bromine  reagent  produces  a  precipitate  which  will 
not  crystallize,  the  remaining  portion  of  the  solution  may  be  ren- 
dered alkaline,  and  the  alkaloid  again  extracted  by  chloroform. 
This  fluid  may  now,  upon  spontaneous  evaporation,  leave  the  alka- 
loid, if  present  in  very  notable  quantity,  in  the  crystalline  state. 
A  portion  of  the  residue  may  be  submitted  to  the  physiological  test 
for  the  alkaloid. 


DATURINE.  047 

Oil  applying  tlio  niotliod  now  considered  to  the  oxiunination  of 
the  contents  of  the  stoniaciis  of  animals  to  whicli  comparatively 
small  qnantities  of  a  flnid  extract  of  belladonna  had  been  adde<l, 
we  in  every  instance  obtained  perfectly  satisfactory  evidence  of  the 
presence  of  atropine. 

Atropine  may  also  be  recovered  from  organic  mixtures  by  the 
use  of  ctlicr,  the  steps  of  the  process  being  precisely  the  same  as 
when  chloroform  is  employed.  The  alkaloid,  however,  is  much 
less  readily  extracted  from  organic  liquids  by  ether  than  by  chlo- 
roform. 

From  the  Blood. — Absorbed  atropine  may  be  recovered  from  the 
blood  by  acidulating  the  latter  with  sulphuric  acid,  in  the  proportion 
of  about  one  drop  of  the  acid  to  each  fluid-ounce  of  blood,  and 
agitating  it  with  somethino;  more  than  its  own  volume  of  alcohol. 
The  mixture  is  theu  gently  heated  for  about  fifteen  minutes,  and  the 
liquid,  after  cooling,  strained  through  muslin,  and  the  residue  washed 
with  alcohol  and  strongly  pressed.  The  strained  liquid  is  concen- 
trated, at  a  moderate  temperature  on  a  water-bath,  again  strained, 
then  evaporated  to  a  small  volume,  the  filtered  liquid  rendered 
alkaline,  and  the  liberated  alkaloid  extracted  by  chloroform.  If  the 
chloroform  residue  is  not  sufficiently  pure  for  testing,  it  is  extracted, 
in  the  usual  manner,  a  second  time  by  that  liquid. 

Three  fluid-ounces  of  blood,  taken  from  a  doo;  that  had  been 
given  five  drachms  of  Tilden's  fluid  extract  of  belladonna  and  killed 
by  a  blow  on  the  head  one  hour  and  a  half  afterward,  when  exam- 
ined by  the  foregoing  method,  furnished  very  satisfactory  evidence 
of  the  presence  of  atropine.  A  similar  quantity  of  the  extract 
being  administered  to  a  cat,  a  portion  passed  into  the  lungs  of  the 
animal,  and  caused  death  in  less  than  three  minutes.  Five  drachms 
of  blood  taken  from  this  animal  also  furnished  satisfactory  evidence 
of  the  presence  of  the  alkaloid. 

Section   III. — Daturine.     (Stramonium.) 

History. — Daturine  is  the  name  applied  to  the  active  principle, 
or  alkaloid,  of  Thorn-apple,  Jamestoion  iceed,  or  Datura  stramonium. 
The  existence  of  this  principle  was  announced  in  1819  by  Brandes ; 
but  it  was  first  obtained  in  1833  by  Geiger  and  Hesse.  It  is  found 
in  all  parts  of  the  plant,  but  most  abundantly,  it  is  said,  in  the 


648  DATUEIXE. 

seeds  and  fruit.     Its  composition  is  C1-H2.3XO3,  it  being  identical  in 
composition  with  atropine. 

Preparation. — Daturine  may  be  obtained  from  the  braised  seeds 
of  stramonium,  and  other  parts  of  the  plant,  in  the  same  manner  as 
atropine  is  prepared  from  belladonna,  as  heretofore  described  [ante, 
631).  The  proportion  of  the  alkaloid  present  in  the  plant  is,  per- 
haps, about  the  same  as  that  found  in  belladonna. 

Numerous  instances  of  poisoning  bv  stramonium,  more  partic- 
ularly by  the  seeds,  have  occurred,  but,  with  few  exceptions,  they 
have  been  the  result  of  accident.  As  yet  there  seems  to  be  no  in- 
stance in  which  daturine  in  its  pure  state  has  been  taken  as  a  poison. 

Symptoms. — The  symptoms  produced  by  stramonium  are  very 
similar  to,  if  not  identical  in  kind  with,  those  occasioned  by  bella- 
donna. Thus,  they  are  dryness  of  the  throat,  difficulty  of  deglu- 
tition, .dilatation  and  insensibility  of  the  pupil,  headache,  nausea, 
vomiting,  great  thirst,  obscurity  of  vision,  or  total  blindness,  ring- 
ing in  the  ears,  great  anxiety,  hot  skin,  flushed  countenance,  ver- 
tigo, and  wild  delirium^  with  spectral  illusions,  and  tremors  of  the 
extremities,  followed  by  stupor  and  coma.  Occasionally  convulsions 
and  paralvsis  have  occurred,  as  also  a  scarlet  eruption  over  the  skin. 

In  a  case  reported  by  Dr.  J.  G.  Johnson,  of  Brooklyn,  l^.Y.,  a 
boy,  seven  years  of  age,  ate  a  quantity  of  the  green  seeds  of  stramo- 
nium, picking  them  from  the  burs.  The  first  symptoms  observed 
were  impaired  speech,  flushed  face,  twitchings  of  the  fingers,  and  a 
stafrgering  gait.  About  two  hours  and  a  half  after  taking  the  poison 
the  child  was  in  a  state  of  violent  agitation,  and  had  spasmodic  twitch- 
ings of  the  hands,  as  if  affected  with  chorea;  the  pupils  were  enor- 
mously dilated  and  insensible  to  light,  and  there  was  total  blindness ; 
the  face,  especially  around  the  mouth,  was  much  swollen;  the  action 
of  the  heart  was  feeble,  and  the  pulse  could  not  be  counted;  the  lower 
extremities  were  cold,  and  perfectly  powerless.  The  action  of  an 
emetic  now  brought  away  a  quantity  of  the  seeds.  Two  hours  later, 
the  child  was  violently  maniacal,  constantly  catching  at  imaginary 
objects  in  the  air,  was  also  deaf,  and  unable  to  articulate.  These 
symptoms  gradually  abated,  but  it  was  several  days  before  the  patient 
entirely  recovered,  the  insensibility  of  the  pupils  continuing  until 
the  fourth  day.     {Araerican  Medical  Times,  1860,  i.  22.) 

Dr.  H.  Y.  Evans,  of  Philadelphia,  has  reported  an  instance  in 
which  seven  children,  aged  from  six  to  nine  years,  had  each  swallowed. 


PHYSIOLOGICAL   EFFECTS.  G49 

it  is  saiil,  only  ten  of  tlio  seeds.  Four  lioui-s  afterward,  the  j)iij)ils  in 
all  seven  cases  were  dilated  to  their  utmost.  In  three  of  the  children, 
who  had  swallowed  the  seeds  without  chewinLC  them,  dilatation  of  the 
pupils  and  slit^ht  i)erversion  of  vision  were  the  only  eflbcts  observed. 
But  in  the  four  remaining  cases,  in  which  the  seeds  had  been  chewed, 
in  addition  to  the  dilated  state  of  the  pupils  and  ])crverted  vision 
there  was  confusion  of  intellect,  deafness,  intoxication,  full  pulse,  slow 
respiration,  and  entire  loss  of  power  to  direct  the  motions  of  the 
limbs;  these  symptoms  were  succeeded  in  a  few  hours  by  stupor, 
and  in  one  case  by  violent  delirium,  resembling  delirium  tremens. 
Emetics  having  failed  to  act,  except  in  the  three  slight  cases,  the 
stomach  was  emptied  by  means  of  the  stomach-pump,  and  on  the  third 
day  every  vestige  of  the  poisoning  had  disappeared,  the  pupils  being 
the  last  to  yield.     {Amer.  Jour.  lied.  Sci.,  July,  1866,  278.) 

A  somewhat  similar  instance  to  that  just  cited  has  been  reported 
by  Dr.  A.  P.  Turner.  {Ibid.,  April,  1864,  552.)  Of  seven  children 
who  had  eaten  a  quantity  of  the  seeds,  in  five  vomiting  Avas  early 
produced,  and  they  were  but  slightly  affected.  In  the  other  two, 
the  most  violent  sympforas  with  wild  delirium  manifested  them- 
selves; but,  under  the  nse  of  emetics,  and  laudanum,  the  patients 
were  quite  well  on  the  third  day.  In  a  case  related  by  Dr.  Calkins, 
a  child,  four  years  of  age,  entirely  recovered  after  having  swallowed 
over  a  tablespoonful  of  the  seeds,  although  they  remained  undisturbed 
in  the  body  for  upwards  of  seven  hours,  when  they  were  partly  ejected 
by  vomiting,  and  afterward  partly  by  purging.  [American  Medical 
Monthly,  Sept.  1856,  220.) 

Dr.  C.  C.  Lee  has  related  an  instance  [Amer.  Jour.  Med.  Sci., 
Jan.  1862,  54)  in  which  three  adults  were  poisoned  by  an  alcoholic 
decoction  of  the  seeds  of  stramonium.  Soon  after  taking  the  poison 
two  of  the  patients  were  speechless,  unable  to  walk,  and  in  a  comatose 
condition  ;  their  faces  flushed  to  an  almost  violet  hue,  the  conjunctivae 
injected,  the  pupils  enormously  dilated  and  insensible,  the  face  and 
upper  extremities  burning  hot,  the  tongue  and  throat  dry,  the  respira- 
tion slow  and  labored,  and  the  pulse  rapid,  very  tense  and  full.  In 
the  other  case,  in  which  a  smaller  quantity  of  the  decoction  had  been 
taken,  the  skin  was  of  a  scarlet  hue  and  hot,  the  pupils  dilated,  the 
tongue  parched,  the  respiration  hurried,  the  pulse  very  rapid,  and 
fluttering,  and  there  was  intense  thirst,  with  violent  delirium,  the 
patient  constantly  pursuing  with  her  liands  imaginary  objects  in  the 


650  DATUEINE. 

air,  or  picking  at  the  bedclothes.  About  an  hour  and  a  half  after 
the  poison  had  been  taken,  active  treatment,  including  the  use  of  tlie 
stomach-pump,  was  resorted  to,  under  which  all  the  patients  rapidly- 
recovered. 

In  a  fatal  case,  quoted  by  Dr.  ChrLstison  [On  Poisons,  646),  in 
which  a  child,  aged  two  years,  had  swallowed,  without  chewing, 
about  one  hundred  of  the  seeds,  the  following  symptoms  were  ob- 
served. The  child  soon  became  fretful  and  like  a  person  intoxicated  • 
in  the  course  of  an  hour  eiforts  to  vomit  ensued,  together  with  flushed 
face,  dilated  pupils,  incoherent  talking,  and  afterward  wild  spectral 
illusions  and  furious  delirium.  In  two  hours  and  a  half  there  was 
loss  of  voice  and  the  power  of  swallowing ;  then  croupy  breathing 
and  complete  coma  set  in,  with  violent  spasmodic  agitation  of  the 
limbs,  occasional  tetanic  convulsions,  warm  perspiration,  and  an  im- 
perceptible pulse.  Subsequently  the  pulse  became  extremely  rapid, 
the  abdomen  tympanitic,  and  the  bladder  paralyzed,  but  there  were 
frequent  inv^oluntary  stools ;  and  death  took  place  twenty-four  hours 
after  the  poison  had  been  taken.  At  an  early  period  in  the  case, 
twenty  of  the  seeds  were  discharged  by  an  emetic;  and  afterward 
eighty  by  purging :  none  were  found  in  the  alimentary  canal  after 
death.  In  another  case,  a  decoction  of  about  one  hundred  and 
twenty-five  of  the  seeds  proved  fatal  to  an  elderly  woman  in  seven 
hours.  In  a  case  related  by  Dr.  Allan,  an  unknown  quantity  of  the 
seeds  caused  the  death  of  a  healthy  man  in  about  seven  hours  and  a 
half.  {Lancet,  London,  Sept.  1847,  298.)  Three  non-fatal  cases  of 
stramonium  poisoning  in  children  have  recently  been  reported  by 
Dr.  Herbert  Terry.    {Boston  Med.  and  Surg.  Jour.,  Feb.  1882, 123.) 

The  external  application  of  stramonium  to  a  blistered  surface 
has  in  several  instances  given  rise  to  alarming  symptoms.  In  one 
instance,  the  extract  employed  as  a  suppository  induced  many  of 
the  symptoms  of  delirium  tremens.  Even  bruising  the  leaves  in  a 
mortar  has  caused  dilated  pupil  and  irritation  of  the  skin.  {BecFs 
Med.  Jur.,  ii.  877.) 

T'EEATMEXT. — This  is  the  same  as  in  poisoning  by  belladonna 
{ante,  63^8).  In  a  case  of  stramonium  poisoning  quoted  by  Dr.  A. 
Stille  {2Iat.  Med.,  i,  754),  one  grain  of  morphine  hydrochloride  was 
administered  every  hour,  and  eight  grains  were  taken  before  any 
result  was  perceived.  After  the  eighth  dose  slight  signs  of  awaken- 
ing consciousness  were  visible,  but  the  pupil  still  remained  widely 


CHEMICAL    PROPERTIES.  051 

dilated.  Subsequently,  as  the  syniptoins  abated,  the  intervals 
between  the  doses  were  lengthened,  but  in  the  course  of  eighteen 
hours  fifteen  gra'mx  of  the  morphine  salt  were  taken. 

PosT-jroRTKM  Appearances. — In  the  cjise  of  the  child,  here- 
tofore cited,  in  which  death  occurred  in  twenty-four  hours,  the  brain 
Avas  found  natural,  the  stomach  and  intestines  healthy,  the  bladder 
distended,  the  larynx  and  oesophagus  slightly  reddened,  the  rima 
glottidis  thickened  and  very  turgid,  and  the  blood  throughout  the 
body  semi-fluid.  In  Dr.  Allan's  case,  nineteen  hours  after  death, 
there  was  found  great  turgcscence  of  the  membranes  of  the  brain  ; 
the  brain  itself  was  firm  and  highly  injected,  the  choroid  plexus 
turgid,  and  the  ventricles  contained  a  little  bloody  serum.  The 
lungs  were  very  vascular,  and  the  heart  flaccid.  The  stomach  con- 
tained about  four  ounces  of  ingesta,  in  which  were  found  eighty- 
nine  entire  seeds  of  stramonium,  together  with  many  fragments. 
The  mucous  membrane  of  the  stomach  throughout  was  slightly 
congested,  and  presented  two  patches  of  extravasation,  the  one  being 
in  the  greater  curvature  of  the  organ,  and  the  other  near  the  pyloric 
orifice.  Many  of  the  poisonous  seeds,  as  well  as  fragments,  were 
also  found  throughout  the  entire  length  of  the  small  intestines.  The 
liver,  spleen,  pancreas,  bladder,  and  kidneys  were  normal. 

Chemical  Properties. 

Daturine  is  not  only  identical  with  atropine  in  regard  to  its  ele- 
mentary composition,  but  is  also  possessed,  as  first  announced  by 
Planta  {C'hem.  Gaz.,  1850,  350),  of  the  same  physical  and  chemical 
properties.  The  chemical  reactions  of  atropine  and  the  methods  of 
separating  it  from  organic  mixtures,  as  already  described,  are,  there- 
fore, equally  applicable  for  the  detection  of  daturine. 

The  identity  of  these  two  alkaloids,  in  regard  both  to  their  prop- 
erties and  physiological  effects,  is  now  generally  conceded.  Hence 
it  is  obvious  that,  unless  some  compound  is  discovered  to  exist  in  the 
one  plant  that  is  not  present  in  the  other,  there  can  be  no  chemical 
means  of  distinguishing  between  poisoning  by  belladonna  and  by 
stramonium.  This  can  be  done  only  when  portions  of  the  plant 
are  found  and  identified  by  their  physical  and  botanical  characters, 
or  by  a  knowledge  of  the  attending  circumstances. 

Further,  it  is  now  generally  admitted  that  all  o^  the  mydriatic 
alkaloids  have  the  same  elementary  composition,  namely,  C17H23XO3 ; 


652  DATUEI^^E. 

but  it  is  still  held  by  some  that  at  least  certain  of  them  differ  some- 
what in  their  properties.  According  to  the  recent  researches  of  Prof. 
Landenburg,  there  are  three  distinct  but  closely  allied  principles  of 
this  kind,  namely,  Atropine,  ffyoscy amine,  and  Hyoscine.  Under 
the  name  Hyoscy amine  he  includes  as  fully  identical  the  alkaloids 
formerly  known  as  kyoscyamine,  daturine,  and  duboisine,  tiie  first 
derived  from  Hyoscyamus  niger  (henbane),  and  the  last-named  from 
Duboisia  myojooroides.  Hyoscine  is  found,  according  to  Prof  Lan- 
denburg, only  in  Hyoscyamus  niger,  associated  with  hyoscyamine. 

On  examining  comparatively  samples  of  atropine,  daturine,  hyos- 
cyamine, and  duboisine,  as  prepared  by  well-known  manufacturers, 
we  in  no  instance  found  any  essential  difference  in  their  chemical 
properties  with  reagents.  Thus,  they  all  gave  similar  crystalline 
precipitates  with  bromine,  and  the  same  color  reaction  under  Vitali's 
test,  and  like  results  with  other  reagents. 

Extraction  from  Aqueous  Mixtures. — When  one  grain  of  daturine 
was  dissolved,  by  tlie  aid  of  a  gentle  heat,  in  four  hundred  grains  of 
pure  water,  and  the  solution  agitated  with  four  volumes  of  chloro- 
form, this  liquid  left  upon  spontaneous  evaporation  0.88  of  a  grain 
of  the  pure  alkaloid.  When  a  similar  aqueous  solution  was  agitated 
with  four  volumes  of  absolute  ether,  this  fluid  extracted  0.80  of  a 
grain  of  the  alkaloid.  On  extracting  alkaline  complex  organic 
mixtures  containing  small  quantities  of  a  fluid  extract  of  stramo- 
nium, by  chloroform,  we  obtained  about  the  same  results  as  already 
described  from  similar  mixtures  containing  the  extract  of  belladonna. 

One  ounce  of  blood,  taken  from  a  cat  killed  by  half  an  ounce  of 
Tilden's  fadd  extract  of  stramonium,  when  subjected  to  the  same 
treatment  as  described  far  the  recovery  of  atropine  under  similar 
circumstances,  furnished  a  final  chloroform  residue  which  gave  un- 
equivocal evidence  of  the  presence  of  the  alkaloid. 


VERATRINE.  C53 


OHAPTEE  Y. 

VEltATRINE,    JERVINE,    SOLANINE. 
Section  I. — Veratrine.     Jervine.    (White  and  American  Hellebores.) 

History. —  Veratrine  is  a  higlily  poisonous  alkaloid,  found  in 
Verairum  sabadilla,  and  in  Cevadilla,  the  seeds  of  Asagrsea  officinalis  ; 
also  in  Veratrum  album,  or  White  hellebore,  and  Veratrum  viride, 
or  American  hellebore.  This  alkaloid  was  first  obtained  from  saba- 
dilla by  Meissner,  of  Germany,  in  1819;  and  about  the  same  time, 
from  the  same  source,  by  Pelletier  and  Caventou,  of  France.  In 
1820,  the  latter  chemists  obtained  from  the  rhizoma  of  Vcrabnim 
album  an  alkaloid  which  they  regarded  as  identical  with  veratrine; 
and  in  1838,  Mr.  Worthington  announced  its  existence  in  the  root 
of  Vei'atrum  viride. 

In  1862,  Mr.  G.  J.  Scattergood  announced  that,  in  addition  to 
veratrine,  Veratrum  viride  contained  another  principle  similar  in 
nature  to  that  alkaloid,  but  insoluble  in  ether,  and  a  third  substance, 
a  resin  to  which  the  sedative  action  of  the  drug  was  chiefly  due. 
{Amer.  Jour.  Pharm.,  1863,  74.)  On  the  other  hand,  Mr.  C.  Bul- 
lock claimed  {ibid.,  1865,  321)  that  the  alkaloid  in  question  was  not 
identical  with  veratrine,  and  that  the  resin  of  Scattergood  owed  its 
activity  to  the  presence  of  another  alkaloid,  which,  unlike  the  first, 
was  insoluble  in  ether.  Prof.  Geo.  B.  Wood  named  these  substances 
respectively  veratroidia  and  viridia.  In  1872,  Dr.  Peugnet  announced 
[Med.  Record,  May,  1872,  121)  that  Bullock's  viridia  was  identical 
with  jervine,  first  obtained,  in  1837,  by  E.  Simon  from  Veratrum 
album. 

Much  discrepancy  has  also  existed  in  regard  to  the  active  prin- 
ciple or  principles  of  Veratrum  album.  Thus,  in  1820,  as  already 
mentioned,  Pelletier  and  Caventou  obtained  from  this  plant  an  alka- 
loid which  they  regarded  as  identical  with  veratrine  from  sabadilla 


654  VEEATEINE. 

seeds;  and  in  1837,  Simon  announced  the  presence  of  a  second 
principle,  which  he  named  jervine.  In  1872,  Dr.  Peugnet  claimed 
that  the  alkaloid  other  than  jervine  in  white  hellebore  was  not 
veratrine,  but  identical  with  Bullock's  veratroidia  from  American 
hellebore;  while  still  later,  Mr.  C.  L.  Mitchell  [Proo.  Amer.  Pharm. 
Assoc,  1874,  436)  claimed  that  it  differed  from  both  veratrine  and 
veratroidia,  and  proposed  for  it  the  name  veratralbia.  In  1876  we 
obtained  from  both  Verairum  viride  and  Veratrum  album  an  alkaloid 
which  fully  responded  in  its  reactions  to  all  the  tests  for  veratrine. 
{Amer.  Jour.  Pharm.,  1876,  1.) 

More  recently,  the  alkaloids  of  the  Veratrums  have  been  very 
fully  examined  by  Messrs.  Wright  and  Luff.  [Jour.  Chem.  Soc, 
1879,  405.)  According  to  these  observers,  Veratrum  album  contains 
jervine,  pseudojervine,  rubijervine,  and  veratralbine,  with  a  minute 
quantity  of  veratrine;  whilst  Verat7^um  viride  contains  these  same 
principles  with  the  addition  of  cevadine  (Merck's  veratrine).  The 
proportions  of  these  several  alkaloids  found  in  the  two  Veratrums 
per  kilo,  of  the  roots  were  about  as  follows  : 

V.  albuin.  V.  viride. 

Jervine,  C26H37NO3    ....   1.3   gram.  0.2   gram. 

Pseuclojervine,  CggH^gNO^ 


Kubijervine,  CjgH^NOj 
Veratralbine,  C^gH^NOj 
Veratrine,  C3-H53NO11 
Cevadine,  CmH.qNOq 


0.4       "  0.15     " 

0.25     "  0.02     " 

2.2       "  only  traces. 

0.05     "  less  than  0.004. 

apparently  absent.  0.43  gram. 

4.20  0.80 


According  to  Wright  and  Luff,  sabadilla  seeds  contain  three 
alkaloids,  veratrine,  cevadine,  and  cevadilline,  the  last  being  present 
in  only  small  quantity  and  having  the  composition  CgiHggNOg. 

Preparation,  a.  Veratrine. — For  commercial  purposes,  veratrine 
is  usually  obtained  from  the  seeds  of  sabadilla,  or  cevadilla,  as  it  is 
frequently  called.  The  bruised  seeds,  deprived  of  their  capsules, 
are  exhausted  by  repeated  portions  of  hot  alcohol,  the  mixed  alcoholic 
solutions  concentrated  to  a  small  volume,  then  treated  with  slight 
excess  of  ammonia,  and  the  impure  precipitated  alkaloid  washed  with 
cold  water;  it  is  then  boiled  for  some  little  time  with  water  acidu- 
lated with  hydrochloric  acid  and  containing  animal  charcoal,  the 
cooled  solution  filtered,  the  concentrated  filtrate  rendered  slightly 
alkaline  by  ammonia,  the  precipitate  thus  produced  washed  with 


JERVINE.  655 

water,  and  tlien  dried  on  a  water-ljatli.  The  product  thus  obtained 
niav  be  further  purilicd  by  dissolving  it  in  water  acidulated  with 
liydrochloric  acid,  and  extracting  the  ibreigu  organic  matter  by  ether: 
after  decanting  this  liquid,  the  aqueous  solution  is  treated  with  slight 
excess  of  ammonia,  and  ti)e  liberated  alkaloid  extracted  by  fresh 
ether,  which  is  allowed  to  evaporate  spontaneously,  when  the  vera- 
trine  will  be  left  in  its  very  nearly  pure,  but  amor{)hous  or,  at  most, 
granular,  state. 

Instead  of  the  use  of  alcohol  for  the  extraction  of  the  alkaloid 
from  the  bruised  seeds,  Dr.  Thomson,  of  Edinburgh,  has  proposed 
to  treat  them  with  boiling  water  acidulated  with  hydrochloric  acid, 
and  allow  the  whole  to  stand  twenty-four  hours.  The  liquid  is  then 
expressed,  filtered,  concentrated  to  a  small  volume,  and  treated  with 
slight  excess  of  ammonia.  The  precipitate  thus  produced  is  collected 
on  a  filter,  washed,  and  dried,  then  pulverized  and  extracted  with 
hot  alcohol.  The  alcoholic  solution  is  distilled  until  the  spirit  is 
entirely  expelled,  the  residue  heated  witli  acidulated  water  and  animal 
charcoal,  and  the  filtered  solution  rendered  slightly  alkaline  by  am- 
monia, when  the  veratrine  will  be  precipitated  in  the  form  of  a  nearly 
pure-white  powder.  {Chemical  News,  June,  1861,  334.)  By  this 
method  Dr.  Thomson  obtained  at  the  rate  of  twenty  grains  of  the 
alkaloid  from  one  avoirdupois  pound  of  the  seeds.  From  one  pound 
avoirdupois  of  the  dried  root  of  Veratrum  viride  Mr.  G.  J.  Scatter- 
good,  of  Philadelphia,  obtained  about  thirty  grains  of  nearly  pure 
mixed  alkaloids. 

b.  Jervine. — Jervine  may  be  obtained  from  Veratrum  viride  by 
preparing  a  strong  alcoholic  solution  of  the  roots  and  treating  this 
with  several  volumes  of  water.  When  the  resinous  matter  has  de- 
posited, the  clear  liquid  is  evaporated  to  a  small  volume,  filtered, 
and  the  filtrate  treated  with  slight  excess  of  sodium  carbonate.  The 
precipitate  of  the  mixed  alkaloids  thus  produced  is  extracted  with 
ether,  which,  after  decantation,  is  allowed  to  evaporate  spontaneously, 
small  portions  at  a  time,  in  a  deep  glass  capsule.  The  jervine  will 
now  be  found  chiefly  in  the  bottom  of  the  capsule,  in  the  form  of 
bold  groups  of  crystals,  Plate  XIV.,  fig.  3;  while  the  amorphous 
alkaloids  will  remain  chiefly  in  the  u])per  portion  of  the  deposit,  as 
a  more  or  less  yellowish,  transparent,  vitreous  mass. 

The  residue  thus  obtained  is  treated  with  a  little  water  strongly 
acidulated  with  hydrochloric  acid  (1  :  10),  which  will  readily  dissolve 


656  VERATEIXE. 

the  amorphous  alkaloids,  whilst  the  jervine  will  remain  as  hydro- 
chloride. The  mixture  is  transferred  to  a  moistened  filter,  and  the 
jervine  residue  washed  with  a  little  acidulated  water.  The  washed 
residue  is  now  digested  vvMth  sodium  carbonate  solution,  wdien  the 
alkaloid  will  be  set  free.  This  is  collected  on  a  filter,  and  then  dis- 
solved in  a  little  water  strongly  acidulated  with  acetic  acid.  The 
acetic  acid  solution  is  rendered  alkaline  by  sodium  carbonate,  and 
the  liberated  alkaloid  extracted  with  chloroform.  If  the  chloroform 
residue  is  amorphous,  it  may  be  converted  into  the  crystalline  state 
by  moistening  it  with  a  little  diluted  alcohol. 

Poisoning  by  veratrine,  in  its  pure  state,  has  been  of  extremely 
rare  occurrence,  and  as  yet  in  no  instance,  so  far  as  we  know,  has  it 
been  taken  in  fatal  quantity  by  the  human  subject.  But  poisoning 
by  portions  of  some  of  the  different  plants  which  owe  their  activity, 
at  least  in  part,  to  the  presence  of  this  alkaloid,  has  not  unfrequently 
happened,  as  the  result  of  accident.  There  seems  to  be  no  instance 
on  record  of  criminal  poisoning  by  this  substance.  The  ordinary 
medicinal  dose  of  the  commercial  alkaloid  is  about  one-tenth  of  a 
grain. 

Symptoms. —  White  hellebore  root  has  long  been  known  as  a  poi- 
son. When  taken  in  poisonous  quantity,  the  more  usual  effects  are 
a  sense  of  burning  heat  in  the  stomach,  with  a  feeling  of  constriction 
and  heat  in  the  mouth  and  throat,  great  anxiety,  nausea,  violei.t 
vomiting,  purging,  tenesmus,  pain  in  the  bowels,  trembling  of  the 
limbs,  great  prostration,  cold  sweats,  small  and  feeble  pulse,  vertigo, 
dilated  pupils,  loss  of  sight,  impaired  speech,  coldness  of  the  extremi- 
ties, convulsions,  and  insensibility.  These  symptoms  are  never,  per- 
haps, all  present  in  the  same  case.  Thus,  instances  are  recorded  in 
which  purging  was  absent,  and  others  in  which  there  was  no  vomiting. 
This  substance  has  not  unfrequently  occasioned  death.  In  non-fatal 
cases,  the  symptoms  are  sometimes  very  slow  in  disappearing. 

In  an  instance  cited  by  Dr.  Christison,  in  which  three  persons 
had  taken  a  quantity  of  the  root,  and  finally  recovered,  the  following 
symptoms  were  observed.  In  the  course  of  an  hour  all  the  patients 
experienced  a  sense  of  burning  in  the  throat,  gullet,  and  stomach, 
followed  by  nausea,  dysuria,  and  vomiting;  weakness  and  stiffness 
of  the  limbs;  giddiness,  blindness,  and  dilated  pupil;  great  faintness, 
convulsive  breathing,  and  small  pulse.  One  of  them,  an  elderly 
woman,  who  had  taken  the  largest  quantity,  had  an  imperceptible 


PHYSIOLOGICAI.    EFFECTS.  007 

pulse,  stertorous  breath i n u,  n ml  total  insensibility;  on  tlio  following 
(lay  an  eruption  appeared  over  the  body.  (On  Poisons,  673.)  Two 
children,  aged  three  and  a  half  and  one  and  a  half  years  respectively, 
drank  of  a  decoction  of  white  hellebore.  The  principal  symptoms 
were  violent  vomiting,  insensibility,  a  pale  and  sunken  countenance, 
small  sharp  pulse,  heat  of  head  and  coolness  elsewhere,  slight  spas- 
modic movements  of  the  face  and  limbs,  neck  somewhat  swollen, 
deglutition  impossible,  pupils  dilated,  and  the  eyes  staring.  Both 
children  recovered.     (Stille,  3Iat.  Med.,  ii,  314.) 

Dr.  E.  Peugnethas  very  fully  reported  [Med.  Record,  May,  1872, 
124)  the  case  of  a  young  married  lady,  who  by  mistake  swallowed 
a  quantity  of  a  tincture  of  veratrum  album,  equivalent  to  half  a 
drachm  of  the  powdered  root.  No  symptoms  appeared  for  three 
hours;  but  four  hours  after  taking  the  dose  she  was  found  pulseless, 
the  heart  pulsating  feebly  and  irregularly ;  the  respiration  was  slow. 
The  eyes  were  fixed  and  staring,  the  pupils  dilated,  and  there  was 
almost  total  loss  of  sight.  The  body  was  covered  with  a  cold  and 
clammy  perspiration,  and  there  was  complete  anaesthesia  of  the  skin  ; 
the  lips  were  bright  carmine;  the  mind  was  clear,  calm,  and  col- 
lected ;  there  was  incessant  vomiting  and  retching,  th,e  fluid  ejected 
being  a  viscid,  glairy  mucus,  of  a  greenish  hue.  Shortly  afterward 
there  was  violent  purging  accompanied  with  severe  tenesmus.  Vio- 
lent symptoms  continued  for  several  weeks,  but  finally  the  patient 
fully  recovered. 

In  a  fatal  case,  in  which  a  man  had  taken  only  a  small  quantity 
of  the  powdered  root,  the  patient  was  soon  seized  with  violent  and 
incessant  vomiting,  and  died  within  twelve  hours.  In  an  instance 
quoted  by  Dr.  Taylor  [On  Poisons,  575),  twenty  grains  of  the 
powder  caused  convulsions,  and  death  in  three  hours.  The  external 
application  of  hellebore  to  the  epigastrium  has  caused  violent  vomit- 
ing. So,  also,  its  employment  in  the  form  of  enema  has  given  rise 
to  violent  symptoms. 

American  hellebore,  familiarly  known  as  Indian  poke,  has  not 
unfrequently  produced  alarming  and  even,  in  a  few  instances,  fatal 
results.  All  parts  of  the  plant  have  a  nauseous,  bitter  taste,  fol- 
lowed by  a  persistent  acrid  sensation  n\  the  mouth  and  throat.  The 
symptoms  occasioned  by  an  overdose  of  this  substance  are  very 
similar  to  those  produced  by  white  hellebore.  In  a  case  reported 
by  Dr.  J.  C.  Harris,  of  West  Cambridge,  a  feeble  child,  one  and  a 

42 


658  YEEATEINE. 

half  years  old,  was  ignorantly  given  four  drops  of  the  tincture  of 
veratrum  viride  mixed  with  water  every  half-hour,  until  four  or 
five  doses  had  been  taken,  when  by  mistake  a  dose  containing  about 
sixteen  drops  was  administered.  E^epeated  efforts  to  vomit  ensued 
after  the  administration  of  the  second  dose,  but  without  success, 
except  once,  when  a  small  quantity  of  matter  was  ejected  from  the 
mouth.  Seven  hours  after  taking  the  first  dose  the  child  was  ap- 
parently unconscious,  very  pale,  and  breathing  stertorously ;  the 
pulse  was  very  slow,  the  extremities  cold,  and  a  profuse  perspiration 
covered  the  whole  body.  Treatment  was  now  resorted  to,  but  with- 
out any  attempt  to  remove  the  contents  of  the  stomach.  The  symp- 
toms increased  in  violence,  and  death  ensued  in  about  thirteen  hours 
after  the  first  dose  had  been  given.  [Amer.  Jour.  Jled.  Sci.,  July, 
1865,  284.) 

Dr.  T.  M.  Johnson,  of  Buffalo,  has  related  an  instance  in  which 
he  made  a  post-mortem  examination  of  the  body  of  a  woman  whose 
death  was  stated  to  have  been  produced  by  two  doses  of  Tilden's 
fluid  extract  of  veratrum  viride.  It  seems  that  the  woman,  who  was 
fiftv  years  old  and  quite  infirm,  had  taken  at  first  a  dose  of  about 
thirty  drops  of  the  extract,  and  in  about  two  hours  was  seized  with 
considerable  pain  in  the  stomach,  nausea,  and  vomiting.  From  four 
to  six  hours  after  taking  the  first  dose  she  took  another  and  larger 
one,  probably  about  forty-five  drops.  This  was  followed  within  two 
hours  by  severe  pain  in  the  epigastrium,  retching,  vomiting,  Aveak 
and  rapid  pulse,  and  marked  prostration;  and  within  twelve  hours 
she  had  two  or  three  bloody  stools  with  considerable  tenesmus. 
Diarrhoea  continued  a  few  hours  after  the  subsidence  of  the  dysen- 
teric discharges;  but  the  retching  and  vomiting  continued  at  inter- 
vals for  about  four  weeks,  when  she  died.  Xo  abnormal  appearance 
was  detected  in  the  body,  except  that  the  stomach  was  much  less 
in  size  than  usual.    [Buffalo  Med.  and  Surg.  Jour.,  ^ow  1866, 133.) 

In  an  instance  related  by  Dr.  J.  B.  Buckingham  [Amer.  Jour. 
Med.  Sci.,  Oct.  1865,  563),  two  gentlemen,  through  mistake,  swal- 
lowed each  about  a  teaspoonful  of  a  fluid  extract  of  the  American 
hellebore.  In  about  half  an  hour  one  of  the  patients  was  found 
almost  speechless,  retching  and  vomiting  incessantly,  bathed  in 
profuse  cold  perspiration,  and  with  a  scarcely  perceptible  pulse. 
On  the  administration  of  a  teaspoonful  of  laudanum  the  vomiting 
ceased,  and  the  patient  rapidly  recovered.     In  the  other  case,  in 


PHYSIOLOGICAL    EKFECTS.  G59 

wlilcli  tlic  l:iii(l;miini  wns  not  administered,  the  voinitintr  oontiniiod 
for  some  hours,  with  total  h)ss  of  speech  and  of"  h)comotion  for  some 
time. 

Dr.  Geisen  reports  {}led.  and  Surrj.  lieporier,  Dee.  1870,  4o3) 
tlie  case  of  a  hidy,  aged  sixty  years,  suffering  from  hepatic  distress, 
with  occasional  vomiting,  for  which  were  prescribed  ten  drops  of 
Norwood's  tincture  of  veratruni  viride  every  three  hours.  Although 
vomiting  terribly  after  each  dose,  the  j^atient  continued  taking  the 
medicine  until  six  doses  were  taken.  Siiortly  after  taking  the  sixth 
dose  she  sank  and  died  from  the  effects  of  the  poison.  In  a  case 
related  by  Dr.  M.  Marsh  {ibid.,  May,  1873,  379),  a  man  affected  with 
pleuro-pneumonia  swallowed,  through  ignorance,  thirty-three  minims 
of  the  tincture.  He  was  found  soon  after  pulseless,  insensible,  and 
in  a  cold  sweat,  with  frequent  spasmodic  jerkings  of  tlie  arms,  and 
died  in  convulsions  six  hours  thereafter. 

A  case  of  this  kind,  fatal  in  a  few  hours,  is  reported  by  Dr.  R. 
M.  Kirk  {ibid.,  July,  1879,  63),  in  which  a  man,  aged  thirty  years, 
drank  a  quantity  of  the  tincture  of  veratrum  viride,  mistaking  it 
for  whiskey.  Dr.  G.  Sykes  reports  a  noif- fatal  case  {Louisville  lied. 
Neu's,  1880,  115)  in  which  eighty  minims  of  the  tincture  with  one- 
hundred  and  sixty  minims  of  tincture  of  gelsemiunL  had  been  taken. 
A  case  is  related  in  which  an  ointment  of  veratrum  viride  applied  to 
an  ulcer  on  the  leg  produced  vomiting. 

In  a  recent  case  reported  by  Dr.  L.  X.  Horwitz  [Med.  Times, 
Aug.  1884,  8G3),  a  teaspoonful  of  the  officinal  tincture  of  veratrum 
viride,  given  in  mistake  to  a  patient  convalescing  from  typhoid  fever, 
caused  his  death  some  hours  afterward.  In  this  case  the  fatal  termi- 
nation was  apparently  largely  due  to  the  prostrated  condition  of  the 
patient  at  the  time  the  poison  was  taken. 

Veratrine,  as  found  in  the  shops,  is  subject  to  great  variation  in 
strength.  In  a  case  communicated  to  Dr.  Taylor,  one-sixteenth  of 
a  grain  of  the  alkaloid  nearly  proved  fatal  to  a  lady.  Not  long 
after  the  dose  had  been  taken  the  patient  was  found  insensible,  the 
surface  cold,  the  pulse  failing,  and  there  was  every  symptom  of  ap- 
proaching dissolution.  (On  Poisons,  576.)  In  a  case  mentioned  by 
Dr.  S.  R.  Percy,  a  physician  took,  by  mistake,  thirty  grains  of  the 
crude  alkaloid  prepared  from  veratrum  viride.  It  caused  copious 
vomiting,  followed  by  prostration  and  loss  of  pulse  at  the  wrist; 
but  under  the  free  use  of  stimulating  remedies  the  patient  entirely 


660  VERATEINE. 

recovered  on  the  third  day.  {Prize  Essay,  1864,  76.)  Dr.  C.  P. 
Blake  relates  a  case  [St.  George's  Hosp.  Rep.,  1870,  69)  in  which  a 
woman,  by  mistake,  swallowed  three  grains  of  veratrine,  made  into  a 
liniment  with  glycerine,  chloric  ether,  and  laudanum.  Under  treat- 
ment she  speedily  recovered. 

Experiments. — Two  grains  of  nearly  colorless  commercial  vera- 
trine being  administered  in  solution  to  a  healthy  cat,  the  animal 
was  immediately  rendered  prostrate,  frothed  at  the  mouth,  and  died 
in  less  than  one  minute  after  taking  the  dose.  A  similar  quantity 
given  to  a  second  cat  produced  similar  symptoms,  and  death  in  one 
minute  and  three-quarters.  Three  grains  of  the  same  preparation 
given  to  a  young  dog  caused  immediate  vomiting,  which  was  fre- 
quently repeated,  with  purging,  involuntary  urination,  and  great 
prostration,  followed  by  death  in  two  hours  after  the  administration 
of  the  dose.  Of  another  sample  of  the  commercial  alkaloid,  two 
grains  each  were  given  to  two  small  dogs  without  producing  any 
appreciable  symptom  other  than  slight  prostration,  from  which  the 
animals  soon  recovered. 

Treatment. — This  consists  in  the  speedy  removal  of  the  poison 
from  the  stomach,  and  the  subsequent  exhibition  of  stimulants. 
Opium  has  in  several  instances  been  found  highly  beneficial.  No 
chemical  antidote  is  as  yet  known.  Vegetable  infusions  containing 
tannic  acid  have  been  strongly  advised.  Although  this  vegetable 
acid  forms  with  veratrine  a  compound  that  is  only  very  sparingly 
soluble  in  water,  yet  it  is  very  readily  soluble  in  the  presence  of  a 
free  acid.    In  some  instances  purgatives  may  be  found  highly  useful. 

PosT-MOETEM  APPEARANCES.  —In  the  few  cases  that  have  been 
examined,  in  death  from  this  substance,  the  alimentary  canal  was 
more  or  less  inflamed ;  but  nothing  has  been  observed  characteristic 
of  the  action  of  the  poison.  In  animals  killed  by  commercial  vera- 
trine, Esche  found  the  throat  and  oesophagus  pale ;  the  stomach  and 
bowels  more  or  less  contracted,  and  the  latter  somewhat  reddened ; 
and  the  lungs,  liver,  and  heart  gorged  with  blood.  The  brain 
presented  nothing  abnormal.     (Stills,  Mat.  Med.,  ii.  312.) 

Chemical  Properties. 
a.  Veratrine. 
In  THE  Solid  State. —  Veratrine,  when  perfectly  pure,  is  a  col- 
orless, odorless  solid,  which  may  be  obtained,  not  readily,  however, 


CHEMICAL   rnOPERTIES.  CGI 

ill  the  form  of  transparent  crystalline  prisms.  It  has  an  exceedingly 
acrid  but  not  bitter  tiuste,  followed  by  a  i)ersistent  sense  of  dryness 
and  acridity  in  the  fauces.  When  snuffed  into  the  nostrils,  even  in 
only  very  minute  quantity,  it  occasions  most  violent  and  prolonged 
sneezing;.  As  found  in  the  shops,  veratrine  is  usually  in  the  form 
of  a  dull  white  or  yellowish-white,  amorphous  powder,  having  an 
intensely  acrid,  more  or  less  bitter  taste.  The  impure  alkaloid  is 
much  more  apt,  on  haiulliii<j:,  to  become  diffused  in  the  air  and 
excite  sneezing  than  the  pure  base.  According  to  Dr.  A.  Wright, 
the  sternutatory  constituent  of  Veratrum  viride  is  cevadine. 

AVhen  applied,  in  the  form  of  an  alcoholic  solution,  to  the  sound 
skin,  veratrine  occasions  a  sense  of  heat,  redness,  and  pricking  in 
the  part.  Heated  on  porcelain  or  in  a  glass  tube,  the  pure  alkaloid 
fuses  to  a  brownish  transparent  liquid,  swells  up,  and  is  slowly  dissi- 
pated, under  decomposition,  without  any  residue ;  heated  in  a  direct 
flame,  it  takes  fire  and  barns  with  dense  smoke.  Its  fusing  point, 
according  to  Couerbe,  is  115°  C.  (239°  F.). 

If  a  small  quantity  of  pure  veratrine  be  touched  with  a  drop  or 
t\vo  of  cold  concentrated  sulphuric  acid,  it  assumes  a  yellow  color, 
then  a  reddish  tint,  and  slowly  dissolves  to  a  pinkish  solution,  which 
after  several  minutes  acquires  a  deep  crimson-red  color.  These 
changes  are  brought  about  almost  immediately  by  the  application  of 
heat.  This  is  one  of  the  most  characteristic  reactions  of  veratrine 
yet  known  (see  post). 

Concentrated  hydrochloric  acid  dissolves  the  pure  alkaloid  with- 
out change  of  color;  but  if  the  solution  be  heated  to  the  boiling 
temperature,  as  first  observed  by  Merck  and  afterward  more  minutely 
by  Trapp,  of  St.  Petersburg,  it  quickly  acquires  a  red  color,  which 
ultimately  becomes  very  intense  and  resembles  that  of  a  solution  of 
potassium  permanganate.  Under  this  reaction,  if  only  a  drop  of 
the  acid  be  employed,  almost  the  least  visible  quantity  of  the  alka- 
loid will  manifest  itself.  With  minute  quantities,  the  coloration  is  best 
observed  by  performing  the  experiment  in  a  white  porcelain  dish. 

The  pure  alkaloid  is  also  soluble  without  change  of  color  in 
concentrated  nitric  acid.  But,  under  the  action  of  this  acid,  the 
alkaloid  as  found  in  the  shops  usually  acquires  a  yellow  or  reddish 
color  and  dissolves  to  a  more  or  less  yellowish  solution. 

Veratrine  has  strong  basic  properties,  completely  neutralizing 
even  the  most  powerful  acids  to  form  salts,  but  few  of  which  have 


662  VERATRINE. 

as  yet  been  obtained  in  the  crystalline  state.  The  sulphate,  hydro- 
chloride, tartrate,  and  oxalate  are  said  to  have  been  thus  obtained. 
The  double  salts  of  the  alkaloid  with  mercuric  and  auric  chlorides 
may  be  obtained  crystallized ;  as  also  the  simple  hydrobromide. 
The  uncrystallizable  salts  form  colorless  gum-like  or  vitreous  masses. 
All  the  salts  of  veratrine  have  the  intensely  acrid  taste  of  the  pure 
alkaloid. 

Solubility. — When  large  excess  of  pure  veratrine  was  digested 
for  several  hours,  with  frequent  agitation,  in  pure  water  at  the  ordi- 
nary temperature,  one  part  of  the  alkaloid  dissolved  in  about  7860 
parts  of  the  liquid.  Absolute  ether,  under  the  foregoing  conditions, 
dissolved  the  pure  alkaloid  in  the  proportion  of  one  part  in  108 
parts  of  the  fluid.  Veratrine  is  very  freely  soluble  in  chloroform, 
and  also  in  alcohol.  The  solubility  of  commercial  veratrine  in  these 
different  liquids  is  subject  to  great  variation.  The  alkaloid  is  readily 
soluble  in  water  containing  a  free  acid  ;  but  it  is  only  very  sparingly 
soluble  in  the  caustic  alkalies. 

Extraction. — One  grain  of  pure  veratrine  was  dissolved  by  the 
aid  of  just  sufficient  hydrochloric  acid  in  one  hundred  grains  of 
water,  the  solution  rendered  slightly  alkaline  by  potassium  hydrate, 
and  the  gelatinous  mixture  violently  agitated  with  an  equal  volume 
of  pure  ether ;  this  liquid  was  then  separated  and  allowed  to  evapo- 
rate spontaneously,  when  it  left  a  transparent  vitreous  residue  of 
0.89  of  a  grain  of  the  pure  alkaloid.  Chloroform  under  similar 
conditions  extracted  0.98  of  a  grain  of  the  alkaloid,  which  it  left  on 
spontaneous  evaporation,  in  the  form  of  a  transparent  glacial  mass, 
easily  pulverizable  to  a  highly  electrical  powder. 

The  salts  of  veratrine  are,  for  the  most  part,  freely  soluble  in 
water,  but  insoluble,  or  very  nearly  so,  in  ether ;  they  are  somewhat 
soluble  in  chloroform.  When  one  grain  of  the  alkaloid  in  the  form 
of  hydrochloride  is  dissolved  in  one  hundred  grains  of  water,  and 
the  solution  agitated  with  an  equal  volume  of  pure  ether,  this  fluid 
extracts  0.03  of  a  grain  of  the  salt.  Under  similar  conditions, 
chloroform  extracts  0.31  of  a  grain  of  the  salt,  which  it  leaves,  on 
spontaneous  evaporation,  in  the  form  of  a  colorless,  vitreous  mass. 

Of  Solutioxs  of  Veratrine. — In  the  following  examination 
of  the  behavior  of  solutions  of  veratrine,  as  well  as  in  the  preceding 
investigations,  a  perfectly  colorless  and  partly  crystalline  sample  of 
the  alkaloid  was  employed.     The  solutions  were  prepared  by  dis- 


SULPIIUiaC   ACID   TKST.  663 

solvinti;  the  alUaloid  in  ])iire  water,  bv  tho  aid  of  flic  Ica-st  ])0ssible 
quantity  of"  Iiydrocliloric  acid.  The  tVactions  employed  indicate  the 
fractional  part  of  a  grain  of  tlic  anhydrous  alkaloid  present  in  one 
grain  of  the  solution  ;  the  results,  unless  otherwise  indicated,  refer 
to  the  behavior  of  one  grain  of  the  solution. 

1.  The  Caustic  Alkalies. 

The  caustic  alkalies,  as  also  their  monocarbonatcs,  throw  down 
from  solutions  of  salts  of  veratrine,  when  not  too  dilute,  a  white, 
amorphous  precipitate  of  the  free  alkaloid,  which  is  only  sparingly 
soluble  in  excess  of  the  precipitant,  but  readily  soluble  in  diluted 
acetic  acid.  After  a  time,  especially  if  the  mixture  be  stirred,  the 
precipitate  becomes  more  or  less  granular. 

1.  y-J-jj  grain  of  veratrine,  in  one  grain  of  water,  yields  a  very  copious 

precipitate,   which  after  a  little  time  becomes  converted  into 
small  granules. 

2.  j-j/y-jj-  grain  yields  a  very  good  precipitate,  wliich  is  readily  soluble 

to  a  clear  solution  in  excess  of  the  precipitant. 

3;  -s-qVo  gi*^'»  '•  if  only  a  mere  trace  of  the  reagent  be  added,  the 
mixture  becomes  distinctly  turbid;  if  a  larger  quantity  of  the 
precipitant  be  employed,  the  alkaloidal  solution  remains  clear. 
The  true  nature  of  the  precipitate  produced  by  these  reagents 

may  be  established  by  the  following  test. 

2.  Sulphuric  Acid. 

The  colorless  salts  of  veratrine,  as  well  as  the  free  alkaloid,  when 
treated  in  the  dry  state  with  concentrated  sulphuric  acid,  slowly  dis- 
solve to  a  reddish-yellow  or  pinkish  solution,  which  after  some  minutes 
acquires  a  deep  crimson-red  color.  If  the  mixture  be  gently  heated, 
this  color  manifests  itself  within  a  few  moments,  and  remains  un- 
changed for  some  hours.  The  color  is  slowly  destroyed  by  the  pro- 
longed action  of  heat,  and,  also,  by  stirring  in  the  mixture  a  small 
crystal  of  potassium  dichromate. 

The  following  quantities  of  the  alkaloid  were  obtained  by  evapo- 
rating one  grain  of  a  corresponding  solution  of  the  hydrochloride  to 
dryness  on  a  water-bath. 

1.  Yoi)  g'"'!!"  of"  veratrine,  when  gently  warmed  with  a  drop  of  the 

acid,  quickly  dissolves  to  a  magnificent  crimson  solution. 

2.  YoW  grain  yields  much  the  same  results  as  1. 


664  VERATEINE. 

3.  xo".ToT  gi'ain  :  if  the  veratrine  deposit  be  first  gently  warmed,  and 

then  a  small  drop  of  the  acid  be  allowed  to  flow  over  it,  the  heat 
being  continued,  it  almost  immediately  assumes  a  deep  red  color, 
and  quickly  dissolves  to  a  solution  having  a  quite  distinct  red 
hue. 

4.  -g-o-.-oTo  g^^sij^ :  when  treated  as  under  3,  the  deposit  assumes  a  faint 

reddish  tint,  and  dissolves  to  a  colorless  solution. 

Even  a  much  less  quantity  of  the  alkaloid  than  the  last-men- 
tioned, if  collected  at  one  point  and  touched  with  a  minute  drop  of 
the  warmed  acid,  will  yield  a  very  distinct  coloration. 

Fallacies. — It  has  been  objected  to  this  test  that  several  other 
organic  substances  also  strike  a  red  color  with  sulphuric  acid.  But, 
unless  the  mixture  be  heated  immediately  after  the  application  of 
the  acid,  these  objections  have  no  force,  since  all  these  substances, 
unlike  veratrine,  are  immediately  colored  by  the  cold  acid.  More- 
over, the  colors  thus  produced  differ  in  tint  from  that  occasioned, 
even  after  some  minutes,  by  veratrine.  And,  furthermore,  under  the 
continued  action  of  the  acid  and  heat,  they  diffv^r  greatly  from  the 
alkaloid  under  consideration.  The  exact  behavior  of  the  more  prom- 
inent of  tliese  fallacious  substances  may  be  briefly  mentioned. 

Narceine,  when  touched  with  the  cold  acid,  immediately  assumes 
a  brown  color,  which  quickly  changes  to  brownish-yellow,  then 
slowly  to  greenish-yellow;  if  the  mixture  be  gently  heated,  the 
narceine  quickly  dissolves  to  a  bright,  brownish-red  solution,  which, 
upon  continuation  of  the  heat,  darkens  in  color  and  finally  becomes 
dark  purple-red.  Solanine,  under  the  action  of  the  cold  acid,  imme- 
diately assumes  an  orange-brown  color,  and  very  slowly  dissolves  to 
an  orange  solution,  which,  after  some  hours,  acquires  a  purplish- 
brown  color  and  yields  a  brownish  precipitate ;  if  the  orange-colored 
solution  be  heated,  it  soon  darkens,  becoming  almost  black.  Pip- 
erine  acquires  with  the  acid  an  immediate  orange-red  color,  which 
soon  becomes  brown ;  if  the  mixture  be  heated,  it  immediately  as- 
sumes a  very  dark  brown  color.  Salicine  imparts  to  the  acid  an 
immediate  crimson-pink  hue,  which,  on  the  application  of  a  gentle 
heat,  is  increased  in  intensity,  then  darkens,  and  finally  becomes 
almost  black.  Papaverine  dissolves  in  the  acid  to  an  immediate 
purple  solution,  the  color  of  which  soon  fades ;  on  heating  the 
mixture  the  color  is  quickly  discharged. 

It  must  be  remembered  that  the  intensity  of  the  color  produced 


lUjoMiNi:  IN  iu:«)M(»iivi)inc  acid  Tixr.  6<J5 

by  veratrine  aiul  .sulj)Imric  ac-id  inay  he  more  or  less  mo<lifie(l  by 
the  presence  of  foreign  matter;  and  that  this  is,  perhaps,  never 
wholly  absent  when  the  alkaloid  is  extracted  in  the  ordinary  manner 
from  complex  organic  mixtures. 

3.  Auric  Chloride. 

This  reagent  prodnces  in  solutions  of  salts  of  veratrine  a  canary- 
yellow,  amorphous  precipitate,  which  is  very  sparingly  solul)le,  with- 
out darkening,  in  potassium  hydrate  ;  it  is  also  only  sparingly  soluble 
in  acetic  and  hydrochloric  acids.  Upon  boiling  the  mixture  contain- 
ing the  precipitate,  the  latter  dissolves,  but  is  redeposited  unchanged 
as  the  liquid  cools.  The  precipitate  is  readily  soluble  in  alcohol, 
from  which,  on  slow  evaporation,  it  separates  in  the  form  of  beauti- 
ful groups  of  yellow,  silky  crystals. 

1.  YoT  grain   of  veratrine,  in   one  grain  of  water,  yields   a  very 

copious  precipitate.  If  the  precipitate  from  a  few  grains  of 
the  alkaloidal  solution  be  dissolved  in  a  few  drops  of  alcohol, 
and  the  alcoholic  solution  be  allowed  to  evaporate  slowly,  it 
soon  deposits  very  delicate  crystalline  tufts  and  granules,  Plate 
XIII.,  fig.  3.  The  formation  of  these  crystals,  however,  is 
readily  prevented  by  the  presence  of  foreign  iflatter. 

2.  YoiTo  g^'^iin  yields  a  quite  good  deposit,  which  is  readily  soluble 

to  a  colorless  solution  in  a  few  drops  of  potassium  hydrate,  but 
only  slowly  soluble  in  large  excess  of  hydrochloric  acid. 

3.  -j-o.VjTxr  grain  yields  a  very  distinct  precipitate,  which  is  readily 

soluble  by  heat,  but  reproduced  as  the  mixture  cools. 

4.  sTj-.TiTo  grain  :  the  mixture  becomes  distinctly  turbid. 

4.  Bromine  in  Bromohydric  Acid. 

An  aqueous  solution  of  bromohydric  acid  saturated  with  bro- 
mine occasions  iu  solutions  of  salts  of  veratrine,  and  aqueous  solu- 
tions of  the  free  alkaloid,  even  when  highly  diluted,  a  permanent, 
yellow,  amorphous  precipitate,  which  is  only  sparingly  soluble  in 
diluted  acetic  and  hydrochloric  acids.  The  precipitate  is  readily 
decomposed  by  potassium  hydrate.  Alcohol  dissolves  it  readily, 
and  on  spontaneous  evaporation  leaves  it  in  the  form  of  groups  of 
bold  prismatic  crystals. 
1.  YFo"  grain  of   veratrine,  in  one  grain   of   water,  yields  a  very 


666  VEEATRINE. 

copious,  bright  yellow  precipitate,  the  color  of  which,  on  the 
addition  of  potassium  hydrate,  becomes  white.  The  precipitate, 
when  dissolved  in  alcohol  and  the  liquid  allowed  to  evaporate 
spontaneously,  yields  a  very  good  crystalline  deposit,  Plate 
XIII.,  fig.  4. 

2.  Yo^o"  grain  yields  a  dirty -yellow  precipitate,  which   is  readily 

soluble  to  a  clear  solution  in  potassium  hydrate.  If  the 
precipitate  be  dissolved  in  alcohol  and  the  liquid  evaporated 
spontaneously,  the  deposit  is  left  in  the  crystalline  form. 

3.  -i-o,Vto  gi^^iii  yields  a  greenish-yellow  precipitate. 

4.  -g-g-.-o-oT  grain  •  a  quite  distinct  deposit. 

5.  YoT/ooT  grain  yields  a  very  perceptible  turbidity. 

5.  Iodine  in  Potassium  Iodide. 

An  aqueous  solution  of  potassium  iodide  containing  free  iodine 
throws  down  from  solutions  of  veratrine,  and  of  its  salts,  a  perma- 
nent, amorphous  precipitate,  which  is  soluble  in  alcohol,  but  only 
sparingly  soluble  in  acetic  and  hydrochloric  acids.  The  exact  color 
of  the  precipitate  is  determined  by  the  quantity  of  the  alkaloid 
present. 

1.  yi-g-  grain  of  veratrine  yields  a  very  copious,  reddish-brown  pre- 

cipitate, which,  upon  the  addition  of  potassium  hydrate,  assumes 
a  white  color. 

2.  iQQo  grain  :  a  copious  deposit,  which  is  readily  soluble  to  a  clear 

solution  in  potassium  hydrate. 

3.  Yo'.'roT  gi'ain  yields  a  good,  reddish-yellow  precipitate. 

4.  g-jy.^-o-o-  grain  :  a  distinct,  greenish-yellow  deposit. 

5.  totVot  gi'ain  yields  a  quite  perceptible  cloudiness. 

6.  Picric  Acid, 

An  alcoholic  solution  of  picric  acid  produces  in  solutions  of  salts 
of  veratrine,  when  not  too  dilute,  a  yellow,  amorphous  precipitate, 
which  is  soluble  in  alcohol  and  in  free  acids,  even  acetic  acid. 

1.  yi-g-   grain    of  veratrine,  in  one  grain  of   water,  yields  a  very 

copious  deposit. 

2.  YoVo"  gi'ain  :  a  quite  good,  greenish-yellow  precipitate. 

3.  -g-^oT  gi^ain  yields  a  quite  distinct  turbidity. 


.     .  JEKVIXE.  6G7 

7.  Potassium  Diehromate. 

This  reagent  throws  down  from  concentrated  solutions  of  salts 
of  veratrine  a  vellow,  amorphous  precipitate,  whicli  is  insohihle  in 
excess  of  the  precipitant,  and  only  sparingly  soluble  in  diluted  acids. 
The  precipitate  is  readily  soluble  in  strong  alcohol. 
^-  rou  gi"»in  of  veratrine  yields  a  quite  good  precipitate,  which  after 
a  time  becomes  more  or  less  granular. 

2.  -5-^.  grain  yields  a  very  distinct  reaction. 

3.  Y^-^  grain  :  no  indication. 

Potassium  chromate  produces  a  precipitate  similar  to  that  occa- 
sioned by  the  diehromate,  but  the  reaction  is  somewhat  less  delicate. 

Other  Reagents. — Potassium  sulphoci/anide  and  Potassium  iodide 
throw  down  from  concentrated  solutions  of  salts  of  the  alkaloid  white, 
amorphous  precipitates,  which  are  readily  soluble  in  acetic  acid. 
Platinic  chloride  and  Potassium  ferricyanide  occasion  in  similar  solu- 
tions dirty-yellow  precipitates.  Potassium  ferrocyanide  fails  to  pro- 
duce a  precipitate.  Corrosive  sublimate  throws  down  from  very 
concentrated  solutions  a  white,  amorphous  deposit,  which  is  readily 
soluble  in  water,  and  left,  on  slow  evaporation  of  the  liquid,  in  the 
crystalline  state.  Tannic  acid  occasions  a  white,  flocculent  precipitate, 
even  in  highly  diluted  solutions  of  the  alkaloid. 

b.    Jervine. 

Projjei'ties. — Jervine,  when  pure,  is  an  odorless  solid,  which 
readily  crystallizes  In  the  form  of  colorless,  transparent  needles  and 
prisms,  generally  arranged  in  tufts,  bundles,  and  stellate  groups. 
The  crystals  contain  two  molecules  of  water  of  crystallization,  their 
composition  being,  according  to  Dr.  A.  ^yright,  C26H3-N03,2H20. 
The  anhydrous  alkaloid  melts,  according  to  this  observer,  at  about 
235°  C.  (455°.  F.).  The  molecular  weight  of  the  anhydrous  alka- 
loid is  411. 

Jervine  Is  very  nearly  insoluble  in  water,  and  is  only  moderately 
soluble  in  alcohol.  In  its  crystalline  state  it  is  almost  wholly  in- 
soluble in  ether;  when  mixed  with  the  amorphous  alkaloids  of  the 
plant,  it  is  quite  readily  soluble  in  this  liquid.  Chloroform  readily 
dissolves  the  alkaloid,  and  generally  leaves  it,  on  spontaneous  evapo- 


Q68  JEEVINE. 

ration,  as  a  transparent,  vitreous  mass,  which  immediately  becomes 
crystalline  on  being  touched  with  a  drop  of  alcohol. 

Of  the  salts  of  jervine,  the  acetate  and  phosphate  are  freely  solu- 
ble in  water;  but  tlie  sulphate,  nitrate,  and  hydrochloride  are  only 
sparingly  soluble  in  this  liquid.  According  to  Mr.  Chas.  Bullock, 
the  sulphate  of  jervine  requires  427  parts,  the  nitrate  266  parts,  and 
the  hydrochloride  121  parts  of  water  for  solution.  The  solubility 
of  the  three  last-named  salts  is  greatly  diminished  by  the  presence 
of  the  corresponding  acid  in  its  free  state :  hence  they  may  thus  be 
precipitated  from  their  aqueous  solutions.  Alcohol  dissolves  the 
salts  of  jervine  in  moderate  quantity. 

Reactions  n^  Solid  State. — Concentrated  sulphuric  acid 
causes  pure  jervine  to  assume  a  yellow  color,  and  quickly  dissolves 
it  to  a  yellow  solution,  which,  becoming  reddish-yellow,  then  dirty- 
brown,  finally  assumes  a  bright  green  color.  A  very  minute  portion 
of  the  alkaloid  will  exhibit  this  coloration.  After  a  time  the  green 
color  thus  produced  disappears,  and  dirty-white  or  brownish  flakes 
separate.  These  after  a  time  may  become  more  or  less  granular  or 
crystalline. 

Sulphuric  acid  produces  similar  results  with  the  sulphate,  hydro- 
chloride, and  acetate  of  the  alkaloid ;  but  it  dissolves  the  pure  nitrate 
with  an  orange-red  color,  which  is  more  or  less  permanent  for  Some 
hours. 

Under  the  action  of  sulphuric  acid  containing  a  little  molyhdic 
acid  (Froehde's  reagent),  pure  jervine  yields  about  the  same  green 
coloration  as  with  the  former  acid  alone.  Nor  is  the  green  colora- 
tion much  modified  by  stirring  in  the  sulphuric  acid  solution  of  the 
alkaloid  a  minute  crystal  of  potassium  dichromate. 

Nitric  acid  quickly  dissolves  jervine,  under  a  pinkish  coloration, 
to  a  colorless  solution,  from  which  bold  crystals  of  the  nitrate  may 
separate. 

Hydrochloric  acid  fails  to  produce  any  coloration  or  to  dissolve 
the  alkaloid,  immediately  converting  it  into  the  insoluble  hydro- 
chloride, which  becomes,  partly  at  least,  crystalline. 

SoLUTioxs  OF  Jervine. — Jervine  is  precipitated  from  its  solu- 
tions as  acetate  by  various  reagents. 

1.  Dilute  sulphuric  acid  (1:5)  precipitates  the  alkaloid  as  sul- 
phate, which  is  only  sparingly  soluble  in  the  presence  of  the  free 
acid.     1-lOOth  grain  of  the  alkaloid,  in  one  grain  of  liquid,  yields 


CHEMICAL   PROPERTIES.  C(J9 

an  ininicdiatc  precipitate,  which  quickly  becomes  crystalline,  first 
forming  spherical  nodules,  then  groups  or  brush-like  masses  of 
needles,  and  finally  the  crystals  a&sume  the  forms  illustrated  in  Plate 
XIV.,  fig.  4.  1-oOOth  grain  :  immediately  crystals  begin  to  sepa- 
rate, and  in  a  little  time  there  is  a  very  good  crystalline  deposit. 
1-lOOOth  grain:  microscopic  crystals  soon  appear,  and  after  a  time 
a  very  satisfactory  dejiosit  of  long  needles  separates. 

Soluble  sulphates  also  precipitate  the  alkaloid  from  its  acetic  acid 
solutions. 

2.  Nitric  acid  (sp.  gr.  1.2)  throws  down  the  alkaloid  as  nitrate 
from  solutions  of  the  acetate.  1-lOOth  grain  of  the  alkaloid  yields 
a  dense  precipitate,  quickly  becoming  crystalline,  Plate  XIV.,  fig.  5. 
1-1 000th  grain  :  speedily  groups  of  crystals  appear,  and  after  a  little 
time  there  is  a  very  satisfactory  crystalline  deposit.  On  allowing 
the  liquid  to  evaporate  spontaneously,  a  very  good  crystalline  de- 
posit of  the  nitrate  remains,  usually  in  the  form  of  bold  prisms. 
Crystals  may  be  obtained  in  this  manner  from  even  a  l-10,000th 
solution  of  the  alkaloid. 

Potassium  nitrate,  as  first  obser^'^ed  by  ]Mr.  Bullock,  throws  dowu 
the  same  precipitate  from  solutions  of  jervine. 

3.  Hydrochloric  acid  produces  in  solutions  of  the  alkaloid  a  white 
precij)itate  of  the  hydrochloride,  which  quickly  becomes  crystalline. 
The  limit  of  the  reaction  of  this  acid  is  about  the  same  as  that  of 
nitric  acid. 

The  property  of  yielding  precipitates  with  the  foregoing  mineral 
acids  is  highly  characteristic  of  jervine. 

4.  Ammonia  and  the  fixed  caustic  allcalies  precipitate  the  alka- 
loid as  a  white  deposit,  which  is  insoluble  even  in  large  excess  of 
the  precipitant. 

a.  1-1 00th  grain  yields  a  dense  amorphous  precipitate,  which  is  soon 
changed  into  a  mass  of  short,  delicate  needles. 

h.  1-lOOOth  grain :  a  rather  copious  precipitate,  converted  after  a 
time  into  tufts  of  delicate  needles. 

c.  1-1 0,000th  grain :  soon  long,  delicate  microscopic  needles  appear 
along  the  margin  of  the  drop;    after  a  time  there  is  a  well- 
marked  precipitate. 
The  alkali  carbonates  produce  the  same  precipitates  as  the  free 

alkalies,  only  that  the  reactions  are  perhaps  a  little  less  delicate. 

5.  Bromine  in  bromohydnc  acid  produces  in  solutions  of  the 


670  VEEATEIXE    AND    JERVINE. 

alkaloid,  even  when  highly  dilute,  a  bright  yellow,  amorphous  pre- 
cipitate, which  is  readily  soluble  in  alcohol. 

6.  PlatiniG  chloride  produces  a  deep  yellow  precipitate,  even  in 
solutions  containing  only  1-lOOOth  of  the  alkaloid.  After  a  time 
the  precipitate  becomes  partly  granular  or  crystalline.  The  precipi- 
tate is  readily  soluble  in  alcohol. 

7.  Auric  chloride  occasions  a  light  yellow  precipitate,  which  is 
readily  soluble  in  alcohol.  If  the  precipitate  from  1-1 00th  grain  of 
the  alkaloid  be  not  agitated,  it  after  a  time  becomes  wholly  converted 
into  a  mass  of  brush-like  crystals.  Crystals  may  be  obtained  under 
the  reagent  from  1-lOOOth  grain  of  the  alkaloid. 

8.  Potassium  sulphocyanide  produces  in  a  1 -100th  solution  of 
jervine  a  copious,  white,  amorphous  precipitate,  which  quickly 
assumes  the  crystalline  form.  1-lOOOth  solution  yields  a  good 
crystalline  precipitate. 

9.  Potassium  chromate  produces  in  a  1-lOOth  solution  a  copious, 
yellow,  amorphous  precipitate,  which  after  a  time  becomes  converted 
into  yellow  nodular  masses. 

10.  Picric  acid  throws  down  a  yellow  precipitate,  which  remains 
amorphous.  The  precipitate  is  produced  in  a  1-lOOOth  solution  of 
the  alkaloid. 

Separation  from  Organic  Mixtures. 

Veratrine  may  be  separated  from  complex  organic  mixtures,  as 
the  contents  of  the  stomach,  and  from  the  blood,  in  the  same  manner 
as  already  pointed  out  for  the  recovery  of  atropine  from  similar 
mixtures  (see  ante,  645).  A  portion  of  the  residue  thus  obtained 
from  the  chloroform  extract  is  examined  by  the  sulphuric  acid  test, 
in  the  manner  already  indicated.  Another  portion  may  be  heated 
with  concentrated  hydrochloric  acid.  Any  remaining  portion  may 
then  be  dissolved  in  a  small  quantity  of  water  containing  a  trace  of 
acetic  acid,  and  the  solution,  after  filtration  if  necessary,  examined 
by  some  of  the  liquid  tests.  Should  the  chloroform  residue  contain 
much  foreign  matter,  it  may  be  purified  by  dissolving  it  in  acidulated 
water,  rendering  the  filtered  solution  alkaline,  and  again  extracting 
the  liberated  alkaloid  by  chloroform. 

On  examining,  after  this  method,  the  contents  of  the  stomach 
of  the  first  cat  heretofore  mentioned,  which  had  been  killed  in  less 
than  one  minute  by  two  grains  of  veratrine,  and  also  of  the  young 


KECOVKRY    FROM    ORGANIC    MIXTURES.  671 

(1(%  killed  in  two  hours  by  three  grains  of  the  alkaloid,  we  in  both 
instances  recovered  very  notable  quantities  of  the  poison. 

One  fluid-ounce  of  blood,  taken  from  the  cat  just  nientione<l, 
gave,  when  the  chloroform  residue  was  treated  with  sulphuric  acid, 
very  satisfactory  evidence  of  the  presence  of  the  alkaloid.  This  case 
shows  the  great  rapidity  with  which  the  poison  may  enter  the  circula- 
tion. The  residue  from  six  fluid-drachms  of  blood  from  the  young 
dog,  when  examined  by  sulphuric  acid,  gave  unequivocal  evidence  of 
the  presence  of  the  poison,  the  coloration  being  about  as  well  marked 
as  from  any  quantity  of  the  pure  alkaloid. 

In  poisoning  by  either  Veratrum  viride  or  Yeratrum  album,  the 
jervineof  the  plant  is  more  readily  recovered  from  complex  mixtures 
than  the  veratrine  or  amorphous  alkaloids. 

Experiments. — About  one  drachm  of  a  fluid  extract  of  Veratrum 
viride  being  given  to  a  young  cat,  the  animal  was  immediately 
rendered  prostrate,  and  was  dead  in  about  one  minute  after  the  ad- 
ministration. 

The  contents  of  the  stomach  of  the  oat,  with  the  finely-divided 
tissue  of  the  organ,  were  strongly  acidulated  with  acetic-  acid,  the 
whole  made  liquid  with  water  containing  its  own  volume  of  alcohol, 
and  the  mixture  digested  at  a  moderate  heat  for  half  an  hour.  Tlie 
strained  liquid  was  then  concentrated  to  a  small  volume,  and  filtered. 
The  filtrate  was  treated  with  slight  excess  of  sodium  hydrate,  and 
extracted  by  ether,  which  after  separation  Avas  allowed  to  evaporate 
spontaneously. 

The  residue  left  by  the  ether  contained  a  number  of  groups  of 
crystals  of  jervine.  The  amorphous  alkaloids  were  now  removed 
from  the  residue  by  diluted  hydrochloric  acid,  and  the  jervine  fur- 
ther purified,  when  a  very  notable  quantity  of  the  crystallized  alka- 
loid was  obtained. 

Seven  fluid-drachms  of  blood  taken  from  the  cat  were  acidulated 
with  acetic  acid,  and  thoroughly  agitated  in  a  flask  with  about  two 
volumes  of  diluted  alcohol.  The  mixture  was  then  digested  for  some 
time  at  a  moderate  heat,  the  liquid  strained,  then  concentrated,  and 
filtered.  The  filtrate,  rendered  alkaline,  was  then  extracted  by  ether, 
which,  after  decantation,  was  allowed  to  evaporate,  small  portions 
at  a  time,  in  a  small  capsule. 

Any  jervine  present  in  the  residue  thus  obtained  was  very  care- 
fully dissolved  in  a  little  water  strongly  acidulated  with  acetic  acid, 


672  SOLAXIXE. 

and  the  alkaloid  again  extracted  from  the  alkalized  filtered  liquid 
bv  ether.  The  separated  ether,  on  spontaneous  evaporatiou,  left  an 
amorphous  residue,  which,  on  being  moistened  with  diluted  alcohol 
and  spontaneous  evaporation  of  the  liquid,  was  almost  wholly  con- 
verted into  crystals  of  the  forms  illustrated  in  Plate  XIY.,  fig.  6. 
These  crystals  were  found  to  consist  of  pure  jervine. 

In  another  experiment,  jervine  was  recovered  in  its  crystalline 
state  from  three  ounces  of  blood  taken  from  a  dog  that  had  swallowed 
between  two  and  three  drachms  of  the  fluid  extract  of  Yeratrum 
viride,  the  animal  having  survived  the  effects  of  the  poison  two 
hours. 

Of  all  the  alkaloids,  there  is  none,  according  to  our  experience, 
so  readily  recovered  in  its  crystalline  state  from  the  blood,  when 
carried  to  this  fluid  by  absorption,  as  jervine. 

Section  II. — Solanine.     (Nightshade.) 

History. — Solanine,  or  solania,  is  the  name  given  to  a  poisonous 
alkaloid  found  in  Solanurn  dvJ.camara,  or  AVoody  nightshade,  Solanum 
nigrum,  or  Garden  nightshade,  and  in  several  other  species  of  the 
Solanum  genus  of  plants.  It  was  first  discovered,  in  1821,  by  M. 
Desfosses,  in  the  Solanum  nigrum.  Very  different  formula  have 
been  assigned  to  solanine,  but,  according  to  the  more  recent  analyses 
of  Zwenger  and  Kind,  its  composition  is  Cj^H^XOjg. 

Preparaiion. — Solanine  is  most  readily  obtained,  according  to  M. 
AVackenroder,  from  the  apples  of  the  common  potato,  Solanum  tubero- 
sum. The  slightly  crushed  apples  are  covered  in  a  suitable  vessel 
for  about  fifteen  hours  with  water  containing  sufiicient  sulphuric  acid 
to  give  the  mixture  a  strongly  acid  reaction.  They  are  then  expressed 
and  removed,  and  the  turbid  acid  lic^uid,  with  fresh  portions  of  sul- 
phuric acid,  added  to  two  successive  quantities  of  fresh  apples,  and 
these  macerated  and  removed  as  before.  The  liquid  is  now  allowed 
to  stand  some  days,  then  strained  through  linen,  and  treated  with 
slight  excess  of  powdered  hydrate  of  calcium.  After  about  twenty- 
four  hours,  the  lime  precipitate,  containing  the  solanine,  is  collected 
ou  a  linen  strainer,  dried  in  warm  air,  and  boiled  several  times  with 
successive  portions  of  strong  alcohol,  which  will  extract  the  alkaloid. 
The  united  alcoholic  extracts  are  then  heated,  and,  while  hot,  filtered; 
on  cooling,  the  liquid  will  deposit  most  of  the  alkaloid,  partly  in  the 
form  of  crvstalline  lamince  and  scales. 


PHYSIOLOGICAL    EFFECTS.  673 

By  (lissolvint:;  oixliiiary  solaninc  in  water  by  the  aid  of  liydro- 
chlorio  arid,  precipitatiiif^  by  atninonia,  and  frequent  recrystallization 
from  nearly  absolute  alcohol,  Otto  Graelin  obtained  the  alkaloid  iu 
the  form  of  beautiful,  colorless,  silky  needles  of  considerable  length. 

Some  of  the  plants  which  owe  their  activity  principally,  if  not 
entirely,  to  the  presence  of  this  alkaloid,  have  in  several  instances 
occasioned  death  ;  but  we  are  not  aware  of  any  instance  of  poisoning 
in  the  human  subject  by  the  prepared  alkaloid. 

Sy.mptoms. — Solanum  dulcamara,  or  Bittersweet,  when  taken  in  an 
overdose,  may  give  rise  to  dryness  of  the  mouth  and  throat,  thirst, 
nausea,  headache,  vertigo,  vomiting,  purging,  and  convulsions,  fol- 
lowed in  some  instances  by  death.  A  little  boy,  aged  four  years, 
who  had  eaten  at  least  two  of  the  berries  of  this  plant,  was  seized 
about  fifteen  hours  afterward  with  purging  and  vomiting,  and  sub- 
sequently with  convulsions,  which  continued  during  the  day,  leaving 
the  child  comatose  and  insensible  during  the  intervals.  Vomit- 
ing of  bilious  matters,  having  a  dark-greenish  color,  continued,  and 
during  the  evening  the  convulsions  became  permanent,  and  death 
ensued  in  about  thirty-two  hours  after  the  poison  had  been  taken. 
A  sister  of  the  deceased,  aged  six  years,  who  had  eaten  only  a  single 
berry,  was  seized  with  sickness  and  purging,  from  which,  however, 
she  recovered  without  more  serious  effects.  Another  sister,  still  two 
years  older,  who  had  eaten  two  of  the  berries,  escaped  without  any 
marked  symptom.  {Lancet,  London,  June,  1856,  715.)  In  two 
other  cases,  an  unknown  number  of  the  berries  proved  fatal  to  two 
children.  In  an  instance  cited  by  Dr.  Beck  {3Ied.  Jur.,  ii.  825), 
several  children  who  had  eaten  some  of  the  berries  were  seized  with 
violent  pain  in  the  intestines,  vomiting  and  purging,  and  in  one 
instance  a  profuse  secretion  of  saliva.  Under  active  treatment  they 
all  recovered. 

So,  also,  the  Solanum  nigrum  has  in  several  instances  destroyed 
life.  Two  little  girls,  between  three  and  four  years  of  age,  ate  a 
quantity  of  the  leaves  of  this  plant.  Between  two  and  three  hours 
afterward  they  w^ere  both  seized  with  pain  in  the  bowels,  vomiting, 
great  uneasiness,  picking  at  the  bedclothes,  and  delirium.  On  the 
succeeding  day,  one  of  the  children,  who  had  suffered  for  several 
days  from  relaxed  bowels,  presented  the  following  symptoms :  the 
abdomen  was  much  swollen,  the  pulse  very  frequent  and  scarcely 
perceptible;  the   respiration  was   quiet,  the   face   pale,  the  pupils 

43 


674  SOLANINE. 

strongly  dilated,  and  there  was  great  uneasiness  of  the  body,  picking 
at  the  bedclothes,  and  entire  loss  of  consciousness.  ISTotwithstanding 
active  treatment,  the  child  died,  under  extreme  exhaustion,  during 
the  evening  of  the  same  day.  The  other  child  entirely  recovered  on 
the  second  day.     [Med.-Chir.  Rev.,  Am.  ed.,  Oct.  1860,  380.) 

In  an  instance  quoted  by  Orfila  {Toxicologie,  1852,  i.  313),  three 
children  who  had  eaten  the  berries  of  the  garden  nightshade  were 
seized  with  severe  headache,  nausea,  vertigo,  colic,  tenesmus,  and  copi- 
ous vomiting.  In  one  of  the  children,  these  symptoms  were  succeeded 
by  extreme  dilatation  of  the  pupils,  impaired  vision,  flushed  face,  pro- 
fuse sweating,  intense  thirst,  loss  of  voice,  stertorous  breathing, 
and  tetanic  convulsions,  followed  by  death  in  about  twelve  hours 
after  the  berries  had  been  eaten.  The  two  other  children,  after  suf- 
fering much  the  same  symptoms,  almost  entirely  recovered  ;  but  they 
had  a  relapse,  under  which  they  finally  sunk. 

Mr.  Morris,  of  Merford,  has  related  an  instance  in  which  a  young 
girl,  aged  fourteen  years,  died  from  the  effects  of  eating  the  berries 
of  the  Solarium  tuberosum,  or  common  potato  plant.  The  symptoms 
described  were  great  jactitation,  lividity  of  the  skin,  cold  and  clammy 
perspiration,  hurried  respiration,  and  exceedingly  quick  and  feeble 
pulse ;  the  teeth  for  the  most  part  were  closed,  and  the  patient  was 
constantly  spitting  through  the  closed  teeth  a  viscid  frothy  phlegm. 
There  was  also  loss  of  speech ;  the  tongue  was  covered  with  a  dark 
brown  moist  fur;  the  expression  was  anxious,  and  the  patient  was 
extremely  restless.  Death  took  place  on  the  second  day.  {Med.- 
Chir.  Rev.,  Oct.  1859,  389.)  Dr.  Christison  quotes  an  instance  in 
which  four  persons  were  seized  with  vomiting,  insensibility,  and 
convulsions  after  eating  potatoes  which  had  begun  to  germinate 
and  shrivel.  In  sprouted  potatoes,  according  to  O.  Bach,  solanine 
exists  only  in  the  jpeel  and  that  part  of  the  tuber  from  which  the 
shoot  arises. 

Solanine,  in  its  pure  state,  seems  to  be  much  less  potent  in  its 
effects  than  most  of  the  alkaloids  heretofore  considered.  In  a  series 
of  experiments  instituted  by  M.  Schroff,  and  cited  by  Dr.  Stills 
{Mat.  Med.,  i.  763),  with  this  substance,  administered  to  healthy 
individuals  in  doses  varying  from  one-thirtieth  of  a  grain  to  three 
grains,  he  observed  increased  cutaneous  sensibility,  itching  of  the 
skin,  gaping,  general  numbness,  sleepiness,  slight  tonic  cramps  in  the 
legs,  and  increased  frequency  of  the  pulse,  which  at  the  same  time 


CHEMICAIi    PROPERTIES.  675 

grew  feeble  and  thready  ;  there  was  also  some  dyspnoea  and  oppres- 
sion in  breathing,  with  nausea  and  unsuccessful  efforts  to  vomit; 
the  head  was  hot,  heavy,  and  dizzy,  with  drowsiness,  yet  with  in- 
ability to  sleep;  the  extremities  were  cold,  the  skin  dry  and  itch- 
insj:;,  and  there  was  marked  general  debility  :  the  pupil  remained 
uiK'hanged. 

Treatment. — The  treatment  in  poisoning  by  solanine,  or  any 
of  the  plants  that  owe  their  activity  to  its  presence,  would  consist  in 
the  speedy  removal  of  the  poison  from  the  stomach  by  an  emetic 
or  the  use  of  the  stomach-pump.  Vegetable  infusions  containing 
tannic  acid,  and  stimulants,  might  be  found  useful. 

Post-mortem  Appearances. — In  regard  to  the  morbid  changes 
protluced  by  this  substance,  we  are  not  acquainted  with  any  instance 
in  which  they  have  been  observed  in  the  human  subject. 

Chemical  Properties. 

In  the  Solid  State. — Solanine,  when  perfectly  pure,  may  be 
obtained  in  the  form  of  beautiful  tufts  of  colorless,  delicate,  crystal- 
line needles.  As  usually  met  with  in  the  shops,  it  has  a  more  or  less 
yellow  color,  and  occurs  either  in  the  form  of  an  amorphous  powder 
or  as  crystalline  scales  and  granules.  The  pure  alkaloid  is  destitute 
of  odor,  and  has  a  bitter  taste,  followed  by  an  acrid  sensation  in  the 
throat.  When  gradually  heated  on  porcelain,  it  fuses,  then  turns 
black,  gives  off  dense  white  fumes,  and  leaves  a  solid  carbonaceous 
residue ;  when  heated  in  a  direct  flame,  it  readily  takes  fire,  and 
is  quickly  consumed.  According  to  A.  Helwig,  solanine  may  be 
sublimed  unchanged,  forming  delicate  needles. 

Although  having  only  a  feeble  alkaline  reaction,  solanine  readily 
combines  with  acids,  forming  salts,  several  of  which  have  been  ob- 
tained in  the  crystalline  state.  The  uncrystallizable  salts  usually 
appear  in  the  form  of  transparent,  colorless,  gum-like  masses.  The 
salts  of  solanine  are  odorless,  and  have  the  bitter,  acrid  taste  of  the 
pure  alkaloid. 

Cold  concentrated  sulphuriG  acid,  when  brought  in  contact  with 
pure  solanine,  immediately  causes  it  to  assume  an  orange-brown 
color,  and  slowly  dissolves  it  to  an  orange-yellow  solution ;  if  the 
solution  be  heated,  its  color  is  quickly  changed  to  deep  dark  brown. 
Concentrated  nitric  acid  readily  dissolves  the  alkaloid  to  a  colorless 
solution,  which  after  a  time  acquires  a  rose-red  tint.     This  color  is 


676  SOLANESTE. 

developed  in  considerable  intensity,  if  only  a  drop  of  the  acid  be 
employed,  from  the  1-lOOth  of  a  grain  of  the  alkaloid ;  but  with 
the  l-500th  of  a  grain  the  color  is  only  just  perceptible.  If  the 
nitric  acid  solution  be  heated,  it  acquires  a  faint  yellow  color.  So, 
also,  hydrochloric  acid  dissolves  it  without  change  of  color;  under 
the  action  of  heat  the  solution  throws  down  a  white,  flocculent 
precipitate. 

If  solaniue  be  heated  for  some  time  with  diluted  sulphuric  or 
hydrochloric  acid,  as  first  observed  by  MM.  Zwenger  and  Kind, 
it  is  resolved  into  grape-sugar  and  a  new,  strongly  basic  alkaloid, 
which  these  observers  named  solanidine,  and  which,  especially  as  the 
mixture  cools,  is  deposited  in  combination  with  the  acid  employed 
in  the  crystalline  form.  [Chevi.  Gazette,  xvii.  308.)  According  to 
O.  Gmelio,  this  decomposition  takes  place  with  diluted  sulphuric 
acid  at  a  temperature  of  50°  C.  (122°  F.).  A.  Hilger  assigned  to 
solanidine  the  formula  CjeH^iNOg. 

Solubility. — When  excess  of  finely-powdered  solaniue  is  digested 
in  pure  ivater  at  the  ordinary  temperature,  with  frequent  agitation, 
for  several  hours,  oue  part  dissolves  in  1750  parts  of  the  menstruum. 
The  alkaloid  is  freely  soluble  in  alcohol,  which  on  slow  evaporation 
leaves  it  principally  in  the  form  of  delicate,  silky,  crystalline  needles, 
Plate  XIII.,  fig.  5.  It  is  only  very  sparingly  soluble  in  absolute 
ether,  and  almost  wholly  insoluble  in  chloroform,  requiring  about 
9000  parts  of  the  former,  and  not  less  than  50,000  parts  of  the 
latter  liquid  for  solution.  Amyl  alcohol,  when  frequently  agitated 
with  excess  of  the  powdered  alkaloid  for  several  hours,  dissolves  one 
part  in  1060  parts  of  the  liquid. 

It  is  thus  obvious  that  solaniue  cannot  be  extracted  in  very 
notable  quantity  from  aqueous  mixtures,  either  by  ether  or  chloro- 
form. From  mixtures  of  this  kind,  however,  the  alkaloid  may  be 
separated  by  hot  amyl  alcohol,  or,  better  still,  by  a  mixture  of  ether 
and  alcohol,  in  which  mixture  it  is  rather  freely  soluble.  Thus, 
when  10-lOOths  of  a  grain  of  the  alkaloid,  in  the  form  of  sulphate, 
were  dissolved  in  thirty  grains  of  water,  and  the  solution,  after  the 
addition  of  slight  excess  of  potassium  hydrate,  agitated  with  five 
volumes  of  a  mixture  of  two  parts  of  absolute  ether  and  oue  part 
of  pure  alcohol,  the  mixture  extracted  9-lOOths  of  a  grain  of  the 
pure  alkaloid,  which  on  spontaneous  evaporation  it  left  in  the  crys- 
talline form. 


OHEMICAL   PROPERTII-S.  fJ77 

The  salts  of  solaninc  arc,  for  the  most  part,  readily  soluble  in 
water;  but  they  are  insoluble  in  chloroform  and  in  ether.  Either 
of  the  latter  liquids,  therefore,  may  be  employed  to  separate  foreign 
organic  matter  from  aqueous  solutions  of  salts  of  the  alkaloid. 

Of  Solutions  of  Solanine.— In  the  following  investigations, 
in  regard  to  the  behavior  of  solutions  of  solanine,  a  sample  of  color- 
less crystallized  solanine  prepared  by  E.  Merck,  of  Darmstadt,  and 
a  purified  specimen  of  the  commercial  alkaloid,  were  employed,  the 
former  being  dissolved  in  the  form  of  sulphate,  and  the  latter  as 
chloride.  Merck's  preparation  was  in  the  form  of  delicate  crystal- 
line needles  and  thin  transparent  laminae.  The  fractions  employed 
indicate  the  fractional  part  of  a  grain  of  the  anhydrous  alkaloid 
present  in  one  grain  of  water;  and  the  results,  unless  otherwise  in- 
dicated, refer  to  the  behavior  of  one  grain  of  the  solution.  One 
grain  of  a  1-lOOth  aqueous  solution  of  solanine  in  the  form  of  sul- 
phate, when  allowed  to  evaporate  spontaneously,  deposits  the  alka- 
loidal  salt  chiefly  in  the  form  of  groups  of  delicate  acicular  cr^^stals, 
Plate  XIII.,  fig.  6. 

1.  The  Alkalies  and  Alkali  Carbonates. 
The  caiistic  alkalies  and  their  monocarbonat^s  throw  down  from 
concentrated  solutions  of  salts  of  solanine  a  colorless,  transparent, 
gelatinous  precipitate  of  the  free  alkaloid,  which  is  readily  soluble 
in  excess  of  the  fixed  caustic  alkalies,  but  only  sparingly  soluble  in 
ammonia,  and  nearly  wholly  insoluble  in  the  alkali  carbonates. 
The  precipitate  is  readily  soluble  in  free  diluted  acids. 

1-  TW  g^'^ii"  of  solanine,  in  one  grain  of  water,  when  treated  with 

a  small  quantity  of  either  of  the  above  reagents,  yields  a  nearly 
solid  gelatinous  mass. 

2-  3T(r  grain,  when  treated  with  a  small  quantity  of  ammonia,  yields 

a  very  good  flocculent  precipitate.  On  account  of  the  ready 
solubility  of  solanine  in  the  fixed  caustic  alkalies,  it  is  difficult 
to  obtain  a  precipitate  by  these  reagents  from  a  single  drop  of 
a  l-500th  solution  of  the  alkaloid. 

^-  TFoT  grai" ;  under  the  action  of  a  trace  of  ammonia,  the  mixture 
becomes  very  distinctly  turbid,  and  after  a  time  yields  a  distinct 
precipitate. 
The  true  nature  of  the  precipitate  produced  by  either  of  these 

reagents  may  be  established  by  the  following  test. 


678  SOLANINE. 


2.  Sulphuric  Add. 

If  a  small  quantity  of  solanine  or  of  any  of  its  colorless  salts, 
in  the  dry  state,  be  treated  with  a  few  drops  of  cold  concentrated 
sulphuric  acid,  the  deposit  immediately  assumes  an  orange-brown 
color,  and  slowly  dissolves  to  a  yellow  or  orange-yellow  solution, 
which  after  about  an  hour  acquires  a  purplish-brown  color  and 
throws  down  a  brownish  precipitate;  after  several  hours,  the  solu- 
tion becomes  colorless  and  the  precipitate  assumes  a  yellowish  or 
dirty-white  color.  The  intensity  of  the  colors  thus  produced  and 
the  time  of  their  development  depend  somewhat  upon  the  quantity 
of  the  alkaloid  present.  Results  similar  to  those  just  stated  are 
obtained  when-  a  drop  of  a  somewhat  concentrated  solution  of  a  salt 
of  the  alkaloid  is  treated  with  several  drops  of  the  acid. 

These  results  are  principally  due,  according  to  Zwenger  and 
Kind,  to  the  solanidine  produced  from  the  solanine  by  the  action  of 
the  acid.  On  treating  different  samples  of  solanine  with  concentrated 
sulphuric  acid,  we  have  frequently  observed  the  peculiar  nauseous 
odor  first  noticed  by  Wackenroder.  When  a  solution  of  solanine 
sulphate  is  evaporated  to  dryness  on  a  water-bath,  the  salt  is  left  in 
the  form  of  a  hard,  transparent,  vitreous  mass,  destitute  of  any 
distinct  crystalline  structure. 

1.  Y^  grain  of  solanine,  in  the  form  of  a  salt,  in  the  dry  state, 

when  treated  with  a  few  drops  of  the  concentrated  acid,  soon 
dissolves,  with  an  orange  color,  to  a  yellow  solution,  from  which 
a  precipitate  soon  begins  to  separate ;  this  increases  in  quantity, 
and  after  a  time  the  liquid  acquires  a  deep  orange,  then  a  bright 
red,  and  finally  a  violet-pink  color,  which  slowly  fades,  and 
after  about  ten  hours  entirely  disappears. 

When  one  drop  of  a  solution  containing  the  1-1 00th  of  a 
grain  of  the  alkaloid  is  treated  with  several  drops  of  the  acid, 
the  mixture  immediately  assumes  a  yellow  color,  and  then 
passes  through  the  changes  just  described. 

2.  xrg-g-  grain,  both  in  the  solid  state  and  when  in  solution,  yields 

much  the  same  results  as  the  preceding  quantity  of  the  alkaloid, 
only  that  the  colors  are  less  intense  and  persistent. 

3.  Yo.Wo  grain :  when  the  dry  deposit  is  touched  with  a  small  drop 

of  the  acid,  it  assumes  a  brownish  color  and  dissolves  to  a  solu- 


POTASSIUM   CHROMATE  TEST.  679 

tioii  liiiving  a  decided  yellow  tint,  which  after  a  time  changes  to 
a  very  faint  reddish  hue. 
4.  ^-(j-.Vau"  &^"^'">  under  the  conditions  just  stated,  dissolves  with  a 
just  perceptible  brownish  tint  to  a  colorless  solution. 

The  production  of  this  series  of  colors,  in  connection  with  the 
formation  of  the  precipitate,  is  quite  characteristic  of  solanine. 
Even  the  1-lOOOth  of  a  grain  of  the  alkaloid,  as  just  pointed  out, 
will  yield  very  satisfactory  results. 

If  a  little  solanine  be  treated  with  a  few  drops  of  a  warm  mix- 
ture of  equal  volumes  of  concentrated  sulphuric  acid  and  alcohol,  as 
first  observed  by  Dr.  Helwig,  a  beautiful  rose-red  color  is  quickly 
developed ;  this  color  may  remain  unchanged  for  several  hours. 
Even  a  very  minute  quantity  of  the  alkaloid  will  manifest  this 
coloration.  This  reaction  is  not  interfered  with  by  the  presence 
of  morphine,  even  in  relatively  large  quantity. 

3.  Iodine  in  Potassium  Iodide. 

An  aqueous  solution  of  potassium  iodide  containing  free  iodine 
causes  somewhat  concentrated  solutions  of  salts  of  solanine  to  assume 
a  deep  orange-red  color,  and  throws  down  an  orange-brown  precipi- 
tate, which  is  unaffected  by  diluted  acids. 

1.  YTS  grain  of  solanine,  in  solution  in  one  grain  of  water,  yields 

the  results  just  stated.  The  precipitate  is  readily  soluble  in 
potassium  hydrate  to  a  colorless  solution,  from  which  after  a 
time  a  dirty-white  precipitate  separates. 

2.  YiJoT  grain  :  an  orange-brown  solution  and  a  slight  precipitate. 

3.  gQ^OQ  grain :  the  mixture  assumes  a  yellowish-brown  color,  but 

fails  to  yield  a  precipitate. 
The  reactions  of  the  first  two  mentioned  solutions  are  peculiar  to 
solanine ;  but  with  more  dilute  solutions  the  results  are  uncertain, 
since  the  reagent  itself  imparts  a  more  or  less  yellowish-brown  color 
even  to  pure  water.  It  must  also  be  borne  in  mind  that  the  reagent 
produces  reddish-brown  precipitates  with  most  of  the  other  alkaloids 
and  with  certain  other  organic  substances. 

4.  Potassium  Chromate. 

This  reagent  produces  in  solutions  of  salts  of  solanine,  when  not 
too  dilute,  a  yellow,  amorphous  precipitate,  which  is  insoluble  in 
excess  of  the  precipitant,  but  readily  soluble  in  acetic  acid.     If  the 


680  SOLAJiflNE. 

mixture  containing  the  deposit  be  treated  with  several  drops  of 
concentrated  sulphuric  acid,  the  precipitate  quickly  dissolves,  and 
the  solution  slowly  acquires  a  bluish  or  bluish-green  color,  which 
remains  unchanged  for  several  hours.  The  production  of  this  color 
is  peculiar  to  the  precipitate  produced  from  solutions  of  solanine. 

1.  yi^  grain  of  solanine,  in  one  grain  of  water,  yields  a  very  copious 

precipitate,  which,  when  treated  with  sulphuric  acid,  undergoes 
the  changes  just  described. 

2.  YWTo  grain  :  the  mixture  immediately  becomes  turbid,  and  after 

a  little  time  yields  a  quite  fair,  yellow,  flocculeut  precipitate. 
If  the  precipitate  be  dissolved  in  a  few  drops  of  sulphuric  acid, 
the  solution  soon  acquires  a  quite  distinct  bluish-green  color. 


1 


grain  :  after  a  time  a  slight  deposit  of  yellowish  flakes. 


"•5  00  0 

Potassium  dichromate  produces  much  the  same  reactions  as  the 
monochromate,  but  the  precipitate  does  not  appear  in  quite  as  dilute 
solutions,  since  it  is  somewhat  soluble  in  the  chromic  acid  eliminated 
by  the  reaction  when  this  reagent  is  employed. 

5.  Bromine  in  Bromohydric  Add. 

An  aqueous  solution  of  bromohydric  acid  saturated  with  free 
bromine  throws  down  from  solutions  of  solanine  salts  an  orange- 
yellow  or  yellow,  amorphous  precipitate,  which  is  sparingly  soluble 
in  diluted  acetic  acid.  After  a  time  the  precipitate  acquires  a  dirty- 
wbite  color,  and  slowly  disappears. 

1.  Yo^  grain  of  solanine,  in  one  grain  of  water,  yields  a  very  copious 

orange-yellow  precipitate. 

2.  YWU^  grain :  a  quite  good,  yellow  deposit. 

3.  g-oVo  gi'^JQ  yields  only  a  just  perceptible  turbidity. 

The  reaction  of  this  reagent  is  common  to  solutions  of  various 
other  organic  substances  besides  solanine. 

Other  Reagents, — Picric  acid  produces  in  concentrated  solutions 
of  salts  of  solanine  a  copious,  yellow,  gelatinous  precipitate,  which 
is  readily  soluble  in  excess  of  the  precipitant.  Tannic  acid  occasions 
a  white,  flocculent  precipitate.  Ammonium  oxalate  and  sodium  phos- 
phate produce,  in  similar  solutions,  white,  gelatinous  precipitates. 

Neither  of  the  following  reagents  produces  a  precipitate,  even  in 
concentrated  solutions  of  salts  of  the  alkaloid :  potassium  sulpho- 


SEPARATION    FROM    ORGANIC    MIXTURES.  681 

cyanide,  potassium  f'erro-  and  ferri-cyanide,  the  chlorides  of  gold, 
platinum,  and  jnilladiuni,  potassium  iodido,  and  free  chromic  acid. 

Separation  from  Organic  Mixtures. 

Although  there  is  no  difficulty  in  identifying  even  a  minute  trace 
of  solanine  when  in  its  pure  state,  yet  when  ])resent  in  only  minute 
quantity  in  complex  organic  mixtures  its  separation  in  a  state  suffi- 
ciently pure  for  testing  is  attended  with  considerable  difficulty,  and 
is  sometimes  impossible,  at  least  by  any  method  at  present  known. 
As  the  alkaloid  is  nearly  wholly  insoluble  both  in  ether  and  in  chloro- 
form, it  is  obvious,  as  heretofore  stated,  that  neither  of  these  liquids 
will  serve  to  separate  it  from  organic  mixtures. 

The  suspected  mixture,  as  the  contents  of  the  stomach,  after 
being  carefully  examined  for  the  presence  of  any  solid  portions  of 
the  poisonous  i)lant,  is  very  slightly  acidulated  with  a  drop  or  two 
of  sulphuric  acid,  and  gently  heated  with  diluted  alcohol  for  about 
half  an  hour.  The  mass  is  then  allowed  to  cool,  transferred  to  a 
linen  strainer,  and  the  strained  liquid  concentrated  on  a  water-bath 
to  a  small  volume,  after  which  it  is  filtered.  The  filtrate  is  evapo- 
rated, at  a  temperature  not  exceeding  49°  C.  (120°  F.),  to  almost 
dryness,  the  residue  well  stirred  with  a  small  quantity  of  pure  water, 
and  the  solution  filtered.  Any  solanine  present  will  now  exist  in 
the  filtrate  in  the  form  of  sulphate,  and  may,  if  not  in  too  minute 
quantity,  be  separated  by  either  of  the  following  methods,  the  first 
of  which  is  based  upon  the  principles  first  applied  by  Wackenroder 
for  the  preparation  of  the  alkaloid,  and  the  second  upon  those  first 
announced  by  Uslar  and  Erdmann. 

According  to  the  first  of  these  methods,  the  clear  filtrate  is  treated 
with  slight  excess  of  powdered  calcium  hydrate,  and  the  mixture 
allowed  to  repose  in  a  cool  place  for  from  twelve  to  twenty-four 
hours,  in  order  that  the  eliminated  solanine  may  completely  subside. 
The  precipitate  is  then  collected  on  a  filter  and  allowed  to  drain, 
then  washed  with  a  small  quantity  of  cold  water  containing  a  trace 
of  ammonium  carbonate,  and,  while  still  moist,  gently  warmed  with 
about  half  an  ounce  of  strong  alcohol,  which  will  dissolve  the  alka- 
loid, whilst  the  calcium  sulphate  and  any  excess  of  caustic  lime 
employed  will  remain,  being  insoluble  in  this  liquid.  The  alcoholic 
solution,  after  filtration,  is  gently  evaporated  to  dryness,  the  residue 
treated  with  a  small  quantity  of  water  very  slightly  acidulated  with 


682  SOLANINE. 

acetic  acid,  and  the  solution  filtered.  A  drop  of  the  filtrate  may 
now  be  examined  by  the  sulphuric  acid  test,  and,  if  it  yields  satis- 
factory evidence  of  the  presence  of  solanine,  other  portions  of  the 
solution  by  some  of  the  other  tests  for  the  alkaloid.  Should,  how- 
ever, the  sulphuric  acid  test  fail,  the  filtrate  is  concentrated  and 
another  drop  examined  in  the  same  manner  before  applying  any  of 
the  other  tests. 

Or,  secondly,  the  filtrate,  supposed  to  contain  the  sulphate  of 
solanine,  may  be  agitated  with  an  equal  volume  of  warm  amyl 
alcohol,  which,  after  the  liquids  have  completely  separated,  is  de- 
canted, and  the  operation  repeated  with  a  fresh  portion  of  the  alco- 
hol. By  this  treatment  much  of  the  coloring  matter  will  be  removed, 
while  the  alkaloidal  salt  will  remain  in  the  aqueous  solution.  This 
solution  is  then  treated  with  slight  excess  of  ammonium  carbonate, 
and  agitated  with  hot  amyl  alcohol,  which  will  now  dissolve  the 
liberated  alkaloid.  The  alcoholic  solution  is  decanted,  the  aqueous 
liquid  washed  with  a  fresh  portion  of  the  hot  alcohol,  and  the  mixed 
alcohols  evaporated  to  dryness  on  a  water-bath.  The  residue  is 
stirred  with  strong,  ordinary  alcohol,  the  solution  filtered  and  evap- 
orated to  dryness.  The  residue  thus  obtained  is  treated  with  a  small 
quantity  of  water  containing  a  trace  of  acetic  acid,  and  the  filtered 
solution  examined  in  the  manner  above  described. 

On  following  the  methods  now  considered,  for  the  examination  of 
complex  organic  mixtures  each  containing  two  drachms  of  Thayer's 
fluid  extract  of  dulcamara, — the  medicinal  dose  of  which  is  from 
half  a  drachm  to  one  drachm, — we  recovered  by  each  a  very  notable 
quantity  of  solanine,  in  its  very  nearly  pure  state,  especially  when 
precipitated  from  the  final  aqueous  solution  by  an  alkali.  The  first- 
mentioned  method  furnished  somewhat  the  best  results;  however, 
the  quantity  of  the  alkaloid  recovered  by  either  process  was  several 
times  more  than  sufficient  to  establish  fully  the  presence  of  the 
poison. 


GELSEMINE.  683 


CHAPTEE    YL 

Gelsemine.     Gelsemic  Acid.     (Yellow  Jessamine.) 

History. —  Gelsemine,  or  gelsemia,  is  the  active  principle  of  Gelse- 
mium  sempei-virens,  popularly  known  as  yellow  jasmine.  Gelsemine 
was  first  obtained  in  its  pure  state,  and  examined  chemically,  by  the 
author,  in  1870.  {Amer.  Jour.  Pharm.,  xlii.  1.)  At  the  same  time 
it  was  shown  that  the  plant  contained  a  non-nitrogenized  principle, 
having  an  acid  reaction,  which  was  named  gelseminic,  or  gelsemic,  acid. 
M.  Sonnenschein  has  claimed  that  this  latter  principle  is  identical 
in  composition  and  chemical  properties  with  the  glucoside  cesculin, 
found  in  the  bark  of  the  horse-chestnut,  and  in  certain  other  barks  ; 
but  we  have  elsewhere  shown  that  this  claim  is  quite  erroneous. 
{Ibid.,  July,  1882.) 

MM.  Sonnenschein  and  Robbins  assigned  to  gehemine  the  com- 
position C11H19NO2;  but,  according  to  A.  W.  Gerrard,  its  for- 
mula is  C12H14NO0,  and  that  of  the  hydrochloride  2C12H14NO,;  HCl. 
[Pharm.  Record,  March,  1883,  67.) 

Preparation. — The  finely-powdered  root  of  the  plant  is  thoroughly 
extracted  with  a  mixture  of  equal  volumes  of  strong  alcohol  and 
water,  and  the  clear  liquid  concentrated  at  a  moderate  heat  to  a 
volume  something  less  than  the  weight  of  the  root  employed.  The 
liquid  is  then  allowed  to  stand  until  the  resinous  matter  has  deposited, 
after  which  it  is  filtered.  The  filtrate  is  treated  with  slight  excess 
of  ammonia,  and  thoroughly  agitated  with  something  more  than  its 
volume  of  rectified  ether,  which  will  readily  take  up  both  the  gelse- 
mic acid  and  the  alkaloid.  The  ether  is  decanted,  and  the  extraction 
repeated  two  or  three  times  with  fresh  portions  of  ether. 

a.  Gelsemine. — The  ether  thus  employed  is  treated  with  slight 
excess  of  hydrochloric  acid,  added  drop  by  drop,  and  the  mixture 
allowed  to  stand  some  hours.     The  alkaloid  will  thus  be  precipitated 


684  GELSEMINE. 

in  the  form  of  the  hydrochloride,  more  or  less  granular  and  crystal- 
line, and  adherent  to  the  sides  of  the  vessel.  After  decanting  the 
ether,  the  residue  is  washed  with  a  little  fresh  ether,  then  dissolved 
in  just  sufficient  water,  and  the  filtered  solution  treated  with  slight 
excess  of  ammonia,  which  will  precipitate  the  greater  portion  of  the 
alkaloid  as  a  pure  white,  curdy  mass.  This  is  quickly  collected  on 
a  filter,  washed  with  a  little  cold  water,  and  allowed  to  dry. 

To  recover  the  gelsemine  still  remaining  in  the  foregoing  filtrate, 
the  latter  is  concentrated,  first  by  a  moderate  heat,  then  spontaneously, 
when  the  alkaloid,  displacing  in  part  the  ammonia  of  the  ammonium 
chloride  present,  will  separate  chiefly  in  the  form  of  bold  groups 
of  prismatic  crystals  of  the  hydrochloride  of  gelsemine,  Plate  XV., 
fig.  1.  These  may  be  washed  with  a  mixture  of  alcohol  and  ether. 
If  the  concentration  has  been  carried  to  dryness,  the  residue  may  be 
washed  with  a  little  water,  to  remove  any  ammonium  chloride  present. 

b.  Gelsemic  Acid. — On  evaporation  of  the  ether  from  which  the 
alkaloid  was  precipitated  by  hydrochloric  acid,  the  organic  acid 
will  be  left  in  the  form  of  comparatively  large  tufts  and  groups  of 
crystals,  Plate  XV.,  fig.  2.  These  are  washed  with  a  little  absolute 
alcohol,  which  will  readily  dissolve,  in  part  at  least,  any  coloring 
matter  present.  The  crystals,  if  still  colored,  may  be  further  purified 
by  dissolving  them  in  hot  alcohol,  which  on  cooling  will  deposit  the 
excess  in  the  form  of  delicate  colorless  needles. 

From  the  dried  root  of  the  plant  we  have  obtained,  as  the 
average  of  several  different  methods  employed,  about  0.25  per  cent, 
of  gelsemine  and  0.5  per  cent,  of  gelsemic  acid.  These  principles 
seem  to  be  present  only  in  the  bark  of  the  root,  the  woody  portion 
being  entirely  free. 

Physiological  Effects. —  Gelsemine  is  an  exceedingly  active  poison. 
One-eighth  of  a  grain  of  the  alkaloid  being  administered  hypodermi- 
cally  to  a  cat,  the  animal  soon  exhibited  signs  of  great  distress,  and 
in  forty  minutes  there  was  great  prostration,  with  difficulty  in  moving, 
the  legs  giving  way,  and  the  movements  being  frequently  backwards. 
The  respiration  became  greatly  reduced,  the  pupils  dilated  to  their 
fullest  extent,  and  death  took  place  in  one  hour  and  a  half  after  the 
poison  had  been  administered. 

One -third  of  a  grain  of  the  alkaloid  administered  subcutaneously 
to  a  rabbit  produced  within  ten  minutes  great  weakness,  then  tremors 
of  the  body,  backward   movements,  violent  clonic  convulsions  in 


PHY8I0IX)QICAL   EPFEOTS.  685 

which  the  animal  turned  a  complete  backward  somersault;  followtd 
by  gasping  respiration  and  death  within  twenty-two  minutes  after 
the  administration.  A  like  quantity  administered  to  a  frog  pro- 
duced similar  symptoms,  with  falling  of  the  jaw  and  death  in  twenty 
minutes. 

Two  grains  of  gelsemic  acid  administered  subcutaneously  to  a 
large  rabbit  produced  no  marked  effect  whatever.  So,  also,  one-fifth 
of  a  grain  produced  no  effect  upon  a  pigeon.  But  one-half  grain 
of  the  acid  being  administered  hypodermically  to  a  frog,  quickly 
produced  deep  fluorescence  of  the  eyes,  great  agitation,  general  pros- 
tration, and  death  in  forty  minutes.  In  another  experiment,  a  like 
quantity  of  the  acid  caused  a  complete  cataleptic  condition  and  death 
within  ten  minutes.  Repeated  experiments  with  varying  quantities 
of  gelsemic  acid  indicated  it  to  be  very  poisonous  to  frogs.  These 
results  confirm  those  previously  obtained  by  Dr.  J.  Ott. 

Gelsemium  Preparations. — The  preparations  of  gelsemium  at 
present  officinal  are  the  fluid  extract,  one  hundred  parts  of  which 
represent  one  hundred  parts  of  the  dried  root ;  and  the  tincture,  one 
hundred  parts  of  which  correspond  to  fifteen  parts  of  the  root.  The 
medicinal  dose  of  the  former  preparation  is  from  two  to  four  minims ; 
that  of  the  latter,  from  fifteen  to  twenty-five  minims. 

The  only  preparation  of  the  drug  officinal  prior  to  the  United 
States  Pharmacopoeia  of  1880  was  the  fluid  extract,  each  fluid-ounce 
of  which  represented  480  grains  of  the  dried  root.  The  tincture 
then  found  in  the  shops  had  usually  one-fourth,  but  sometimes  only 
one-eighth,  the  strength  of  the  fluid  extract.  A  concentrated  tincture 
representing  480  grains  of  the  fresh  root  per  fluid-ounce  was  also 
employed. 

The  present  fluid  extract  is  five  per  cent,  weaker  than  that  for- 
merly directed.  In  a  series  of  examinations  of  various  samples  of 
the  fluid  extract  as  formerly  prejDared,  we  found  it  to  contain  quite 
uniformly  about  0.2  per  cent,  of  gelsemine  and  0.4  per  cent,  of 
gelsemic  acid. 

Poisoning  by  gelsemium  preparations  has  of  late  years  been  of 
not  unfrequent  occurrence,  but  chiefly  as  the  result  of  accident  or 
ignorance,  there  being,  so  far  as  we  know,  only  tw^o  or  perhaps  three 
cases  in  which  it  was  criminally  administered. 

Symptoms. — The  symptoms  produced  by  poisonous  doses  of 
gelsemium  are  impaired  sight,  double  vision,  and  sometimes  total 


686  gelsemhste. 

blindness,  with  falling  and  loss  of  control  of  the  upper  eyelids;  the 
face  is  congested,  and  the  lips  livid,  but  the  face  may  be  pale.  The 
pupils  are  dilated,  and  usually  insensible  to  light;  the  eyes  fixed 
and  more  or  less  staring.  There  may  be  falling  of  the  lower  jaw, 
the  mouth  being  sometimes  wide  open.  Speech  is  impaired  or 
entirely  lost,  and  the  tongue  appears  thick.  The  gait  is  staggering  ; 
the  skin  warm  and  moist,  with  occasionally  free  perspiration.  The 
pulse  is  small,  feeble,  irregular,  and  intermittent,  but  it  has  been 
observed  full  and  strong.  There  is  great  muscular  relaxation,  with 
general  prostration  and  diminished  sensibility,  and  the  extremities 
are  cold.  The  breathing  is  slow,  labored,  spasmodic,  and  sometimes 
stertorous.  Violent  spasms  of  the  throat,  resembling  those  of  hy- 
drophobia, have  been  present  in  a  few  cases.  The  mind  usually 
remains  clear,  but  unconsciousness  has  been  present  even  when 
recovery  followed. 

The  time  within  which  the  symptoms  first  appear  has  varied 
from  a  few  minutes  to  about  two  hours,  but  they  usually  manifest 
themselves  within  half  an  hour.  In  a  case  related  by  Dr.  W.  W. 
Seymour,  in  which  a  teaspoonful  of  the  fluid  extract  of  gelsemium 
was  given  to  a  lying-in  woman  in  mistake  for  ergot,  ten  minutes 
afterward  she  was  extremely  prostrated,  almost  pulseless,  and  the 
respiration  was  failing.  She  finally  recovered.  [Boston  Med.  and 
Surg.  Jour.,  Dec.  1881,  590.)  Dr.  R.  P.  Davis  reports  a  case  in 
which  a  delicate  man,  having  taken  a  tablespoonful  of  Tilden's 
fluid  extract  of  gelsemium,  was  found  soon  after  lying  upon  his  left 
side,  the  face  somewhat  congested,  the  pupils  dilated,  but  respond- 
ing to  light;  eyelids  half  closed,  with  inability  to  move  them;  the 
lower  jaw  drooping,  and  the  tongue  thick ;  his  skin  was  warm  and 
moist ;  the  pulse  small  and  feeble,  and  the  respirations  diminished 
in  number.  An  emetic  being  administered  failed  to  act.  A  little 
later,  the  patient  was  totally  unconscious,  the  pupils  widely  dilated, 
the  breathing  spasmodic,  the  surface  cold  and  congested ;  pulse  almost 
imperceptible,  and  death  took  place  in  two  hours  and  a  half  after 
the  poison  had  been  taken.  (Amer.  Jour.  Med.  Sci.,  Jan.  1867, 
271.) 

In  a  case  reported  by  Dr.  J.  E.  Blake  {New  Yoi^h  Med.  Jour., 
April,  1875),  a  strong  man  took,  by  mistake,  about  two  drachms  of 
the  tincture  of  the  plant.  Besides  the  usual  effects,  such  as  dimness 
of  vision,  prostration,  diminished  action  of  the  heart  and  respiratory 


-  / 


PERIOD    WHEN    FATAL.  687 

organs,  the  patient,  about  Iialf  an  hour  after  taking  the  dose,  had 
synij)toms  closely  resembling  those  observed  in  the  frightful  spasms 
of  ]iy(lro])hobia.  At  short  intervals  the  most  distressing  paroxysms 
of  dyspnoea  occurred,  during  which  he  both  clutched  at  his  throat 
and  beat  the  air  with  his  hands.  lit;  finally  recovered,  being  much 
relieved  by  morphia  hypodermieally  administered.  In  another  in- 
stance, related  by  Dr.  J.  T.  Boutelle  {Boston  Med.  and  Surg.  Jour., 
Oct.  1874,  321),  a  young  man,  aged  twenty-four  years,  suffering  from 
neuralgia,  took  at  1  a.m.  a  teaspoonful  of  the  fluid  extract,  and  in 
fifteen  minutes  repeated  the  dose.  The  pain  was  soon  relieved,  and 
his  eyes  felt  heavy,  and  in  about  half  an  hour  he  complained  of 
choking,  and  soon  arose  struggling  for  breath,  pushing  his  fingers 
into  his  throat,  as  if  trying  to  tear  it  open.  He  staggered,  as  if 
intoxicated,  threw  himself  upon  the  floor,  and  became  unconscious. 
At  4  A.M.  the  respirations  were  gasping,  the  pulse  was  rapid  and 
feeble,  and  the  patient  could  not  be  roused.  The  pupils  were  dilated 
and  insensible  to  light ;  the  body  was  relaxed,  the  lower  jaw  drooping, 
the  skin  moist,  the  extremities  cold,  and,  the  pulse  becoming  slower 
and  weaker,  death  took  place  at  4.45  a.m. 

We  have  elsewhere  reported'  a  case  in  which  three  teaspoonfuls 
of  the  fluid  extract  were  administered  to  a  young,  healthy  married 
woman,  several  weeks  advanced  in  pregnancy.  Tn  two  hours  after 
taking  the  dose,  she  complained  of  pain  in  the  stomach,  nausea,  and 
dimness  of  vision.  These  symptoms  were  soon  followed  by  great 
restlessness,  ineffectual  eiforts  to  vomit,  and  free  perspiration  over 
the  body.  After  five  hours,  the  pulse  was  feeble,  irregular,  and 
intermittent;  there  was  great  prostration,  with  irregular  and  slow 
breathing,  and  the  skin  was  dry.  The  extremities  were  cold,  the 
pupils  dilated  and  insensible  to  light;  the  eyes  were  fixed,  and  con- 
trol over  the  eyelids  was  lost.  The  vital  powers  rapidly  gave  way, 
and  death  occurred  in  seven  hours  and  a  half  after  the  poison  had 
been  taken.     {Amer.  Jour,  Pharm.,  Jan.  1870,  14.) 

Period  when  Fatal. — Of  twenty-five  cases  of  gelsemium  poison- 
ing that  we  have  collected,  thirteen  proved  fatal,  and  the  fatal  period 
varied  from  one  hour  to  seven  hours  and  a  half.  In  a  case  communi- 
cated to  me  by  Dr.  M.  P.  Hatfield,  of  Chicago,  fifteen  grains  of  the 
resinoid  "gelsemin"  proved  fatal  to  a  woman  in  one  hour.  Tlie 
three  following  cases  are  briefly  related  by  Dr.  J.  N.  Freeman,  of 
Brooklyn.    {Lancet,  Sept.  1873,  475.)    A  boy,  three  years  old,  took. 


688  GELSEMINE. 

by  mistake,  about  fifteen  minims  of  tincture  of  gelsemium  (made  by- 
macerating  four  ounces  of  the  root  in  a  pint  of  dilute  alcohol),  and 
died  from  its  effects  in  two  hours.  The  first  symptoms  noticed  were 
double  vision  and  a  staggering  gait,  soon  followed  by  complete  mus- 
cular relaxation.  In  the  second  case,  a  girl,  aged  nine  years,  took 
a  dessertspoonful  of  the  tincture.  Soon  after  taking  the  dose,  she 
complained  of  dimness  of  sight,  double  vision,  and  loss  of  muscular 
power,  and  died  in  less  than  two  hours.  In  the  third  case,  a  boy,  about 
three  years  old,  was  ordered  every  two  hours  a  teaspoonful  of  a  mix- 
ture containing  ten  grains  of  sulphate  of  quinine,  one  drachm  of  tinc- 
ture of  gelsemium,  and  five  drachms  of  syrup.  After  the  first  dose  he 
became  prostrated,  and  staggered  in  walking ;  but  in  due  time  the  dose 
was  repeated.  About  half  an  hour  after  taking  the  second  dose  the 
body  was  perfectly  flaccid,  the  pupils  were  dilated,  there  was  froth 
at  the  mouth,  the  heart  was  beating  feebly  and  slowly,  and  the  pulse 
was  imperceptible  at  the  wrist.    Death  took  place  half  an  hour  later. 

In  a  case  reported  by  Dr.  W.  W.  Seymour,  a  strong  man,  aged 
twenty-eight  years,  took  a  quantity  of  the  tincture,  variously  stated 
from  three  drachms  to  two  ounces,  and  died  from  its  effects,  under 
the  usual  symptoms,  in  six  hours  'after  the  physician  was  called. 
{Boston  3Ied.  and  Surg.  Jour.,  Dec.  1881,  590.) 

Fatal  Quantity. — At  present 4t  is  impossible  to  indicate  the  least 
fatal  quantity  of  this  drug.  Prof.  Seymour,  of  Troy,  states  that  he 
has  seen  repeated  instances  in  which  two  minims  of  the  fluid  extract, 
given  three  times  a  day,  affected  the  sight;  and  four  minims,  three 
times  a  day,  produced  weakness  of  the  legs  and  staggering.  In  a 
case  reported  by  Dr.  Freeman,  cited  above,  a  quantity  of  the  tincture 
equivalent  to  about  twelve  minims  of  the  fluid  extract  proved  fatal 
to  a  boy,  aged  three  years.  And  a  case  is  related  in  which  thirty- 
five  drops  of  a  tincture  of  the  drug  caused  death  in  one  hour  and 
a  half.  A  physician  took,  as  we  are  privately  informed,  a  mixture 
containing  fifteen  minims  of  the  fluid  extract,  and  repeated  the  dose 
at  short  intervals.  After  the  fourth  dose  the  usual  symptoms  of  the 
poison  appeared,  and  terminated  fatally  in  less  than  four  hours.  In 
another  instance,  a  physician,  suffering  from  facial  neuralgia,  took 
ten  minims  of  the  fluid  extract,  and  repeated  the  dose  in  half  an 
hour.  In  fifteen  minutes  after  the  second  dose  there  was  great 
drowsiness,  and  pain  over  the  frontal  region ;  the  pulse  was  weak 
and  intermittent,  the  body  cold  and  shivering;    the  pupils  were 


TREATMENT.  689 

slightly  contracted,  and  there  was  a  general  feeling  of  collapse. 
After  vomiting  freely,  the  patient  rapidly  recovered.  {Med.  Times, 
March,  1881,  382.) 

In  a  case  mentioned  by  Dr.  Seymour,  a  teaspoonful  of  the  fluid 
extract  proved  fatal  to  a  young  lady.  And  in  a  Ciise  already  cited, 
two  teaspoonfuls  of  the  fluid  extract,  given  in  divided  doses,  proved 
fatal  to  a  young  man  in  less  than  four  hours.  Half  a  teaspoonful 
of  a  preparation  of  gelsemiura,  being  given  to  each  of  two  children, 
was  soon  followed  by  the  ordinary  symptoms,  and  death  in  less  than 
three  hours.  [Eckct'iG  Med.  Jour.,  May,  1879,  222.)  Dr.  A.  L. 
Hall  reports  a  case  {Med.  Record,  Jan.  1882,  65)  in  which  a  strong 
woman  took  eight  grains  of  "gelsemin,"  in  two-grain  doses  repeatetl 
every  three  hours,  and  died  from  its  effects  within  an  hour  after 
takinor  the  last  dose.  The  same  writer  cites  three  other  instances  in 
which  two,  three,  and  four  grains  respectively  of  the  same  prepara- 
tion produced  very  alarming  symptoms. 

The  following  cases  of  recovery  may  be  mentioned.  A  lady  took, 
by  mistake,  a  teaspoonful  of  the  fluid  extract.  Dimness  of  vision 
came  on  in  an  hour,  and  was  followed  by  paralysis  of  the  muscles 
of  the  lower  jaw  and  tingling  of  the  extremities.  Five  and  a  half 
hours  later,  she  believed  herself  to  be  dying.  There  was  great  diffi- 
culty in  swallowing,  faintuess,  and  difficult  articulation ;  the  mouth 
was  wide  open  ;  the  pupils  were  greatly  dilated,  and  insensible  to 
light ;  the  pulse  was  rapid  and  feeble.  Under  the  administration 
of  carbonate  of  ammonium,  and  the  use  of  electricity,  she  slowly 
recovered.  (Dr.  F.  W.  Goss,  Boston  Med.  and  Surg.  Jour.,  July, 
1879,  16.)  In  a  case  reported  by  Dr.  R.  P.  Davis,  a  man  recovered 
after  taking  a  teaspoonful  of  the  fluid  extract.  The  treatment  in  this 
case  consisted  of  an  emetic,  which  acted  freely,  followed  by  large  doses 
of  quinine  and  brandy.     {Amer.  Jour.  Med.  Sci.,  Jan.  1867,  271.) 

Treatme2sT. — Xo  chemical  antidote  for  this  poison  is  yet 
known.  The  contents  of  the  stomach  should  be  evacuated  as 
speedily  as  possible,  and  then  internal  and  external  stimulants  em- 
ployed. In  several  instances  the  application  of  electricity  has  been 
found  very  beneficial.  A  striking  instance  of  this  kind  is  reported 
by  Dr.  J.  T.  Main,  who  through  mistake  swallowed  one  drachm  of 
the  fluid  extract  of  gelsemium.  [Boston  Med.  and  Surg.  Jour., 
April,  1869,  185.)  After  a  time  he  became  nearly  blind;  control 
over  the  eyelids  was  almost  entirely  lost ;  the  flexor  muscles  of  the 

44 


690  GELSEMINE. 

hands  and  arms  were  paralyzed,  whilst  the  extensors  were  nearly  so. 
Sensation  in  the  hands  and  arms  was  blunted,  but  not  in  propor- 
tion to  the  loss  of  motion.  The  speech  was  somewhat  affected,  and 
a  very  disagreeable  sensation  was  felt  in  the  head,  even  before  the 
muscles  came  under  the  influence  of  the  drug ;  but  the  mind  was 
clear.  In  this  condition  he  requested  the  poles  of  a  galvanic  battery 
to  be  applied  to  his  hands,  which  being  done,  he  was  instantly 
relieved.  The  relief  was  not  only  instantaneous,  but  perfect  and 
permanent.  Dr.  Main  states  that  he  has  since  tried  the  same  remedy 
upon  persons  pretty  well  under  the  influence  of  gelsemium,  and  with 
like  beneficial  results.  In  a  case  reported  by  Dr.  Seymour,  the 
application  of  electricity  was  attended  with  great  relief  at  first,  but 
the  patient  finally  died. 

The  following  remarkable  case  of  recovery,  in  which  morphine 
was  employed,  is  reported  by  Dr.  G.  S.  Courtright.  {Lancet  and 
Observer,  Cincinnati,  Nov.  1876,  961.)  A  physician  took,  by  mis- 
take, from  one  to  two  teaspoonfuls  of  the  tincture  of  the  drug. 
Within  a  few  minutes  his  vision  was  affected,  and  he  soon  lost  entire 
control  over  the  movements  of  his  head ;  the  breathing  was  slow ; 
the  pulse  rapid  and  feeble.  The  face  was  congested,  the  lips  were 
livid,  the  muscles  of  the  lower  jaw  and  of  the  eyelids  completely 
paralyzed,  the  pupils  dilated,  and  the  eyes  fixed.  Two  hours  after 
the  poison  was  taken,  an  emetic  having  failed  to  act,  about  three 
grains  of  morphine  were  injected  into  the  arm,  in  divided  doses, 
within  a  few  minutes,  and  half  a  grain  was  given  internally.  Very 
quickly  there  was  some  improvement  in  the  breathing ;  the  pupils 
became  slightly  contracted,  the  eyes  less  fixed,  and  there  was  slight 
control  over  the  eyelids.  Soon  after,  the  patient  vomited ;  the  pulse 
became  stronger  and  less  frequent,  the  paralysis  gradually  subsided, 
and  in  two  hours  he  was  able  to  give  an  account  of  the  accident. 
In  Dr.  Blake's  case,  already  cited,  the  hypodermic  use  of  morphine 
was  attended  with  good  results. 

Post-mortem  Appearances. — Nothing  peculiar  has  been  ob- 
served in  the  appearances  after  death  from  poisoning  by  this  sub- 
stance. In  Dr.  Boutelle's  case,  in  which  a  teaspoonful  of  the  extract 
proved  fatal  in  less  than  four  hours,  the  examination  was  made  five 
and  a  half  hours  after  death.  The  body  was  well  nourished ;  rigor 
mortis  marked.  The  blood  was  very  fluid,  of  a  dark  color,  and 
showed  no  tendency  to  coagulate  or  turn  red  upon  exposure  to  the 


GELSEMIC  ACID.  691 

air,  even  after  staiulinir  some  hours.  The  heart,  lungs,  spleen,  and 
kidneys  were  normal.  The  liver  was  dark-colored  and  contained 
nuu-h  liquid  blood.  The  stomach  contained  four  ounces  af  alight- 
colored  fluid  mixture  mixed  with  glairy  mucus.  Its  internal  surface 
was  deeply  congested  and  marked  by  tortuous  dilated  vessels.  The 
intestines  were  normal.  The  brain  was  rather  pale,  and  the  internal 
substance  of  the  lobes  was  dotted  here  and  there  with  small  red  points. 

In  the  case  we  have  elsewhere  reported,  the  body  eight  days 
after  death  presented  the  following  appearances,  as  observed  by  Dr. 
Stephenson.  The  countenance  was  natural ;  cadaveric  rigidity  very 
slight.  The  membranes  and  substance  of  the  brain  and  medulla 
oblongata  were  normal.  The  adipose  tissue  was  thick  and  highly 
tinged  with  bilious  matter.  The  lungs  were  slightly  collapsed,  but 
natural  in  appearance,  and  the  superficial  veins  were  congested. 
The  heart  was  normal  in  size,  the  external  veins  were  injected, 
and  the  cavities  greatly  distended  with  dark  grumous  blood,  inside 
of  which  was  a  well-defined  membranous  deposit.  The  stomach 
contained  a  small  quantity  of  ingesta.  The  peritoneum,  intestines, 
liver,  and  investing  membrane  were  normal.  The  left  kidney  was 
congested. 

The  cases  just  cited  are,  so  far  as  we  know,  the  only  ones  in  w4iich 
the  internal  appearances  in  gelsemium  poisoning  have  been  observed. 
In  Dr.  Hall's  case,  soon  after  death,  the  external  appearances  were 
life-like.  The  skin  was  moist;  the  body  warm,  with  slight  coldness 
of  the  limbs;  the  eyelids  were  drooping,  the  pupils  dilated;  the 
lower  jaw  was  relaxed,  and  the  mouth  presented  an  oval  appearance. 

Chemical  Properties. 

In  poisoning  hj  gelsemium  preparations  the  chemical  examination 
should  be  directed  to  the  recovery  of  both  gelsemic  acid  and  gelsemine, 
especially  as  the  acid  exists  in  the  larger  quantity  in  the  plant,  and 
so  readily  reveals  its  presence  by  its  fluorescent  properties. 

I.  Gelsemic  Acid. — In  its  pure  state  gelsemic  acid  is  a  color- 
less, odorless,  nearly  tasteless  solid,  which  readily  crystallizes,  either 
in  groups  of  prisms  or  tufts  and  single  needles,  or  minute  plates  and 
scales.  It  has  only  a  feeble  acid  reaction,  and  forms  definite  salts 
with    but   few  of  the  metals.      When  gradually  heated  to  about 


692  GELSEMIC    ACID. 

163°  C.  (325°  F.)  it  fuses  to  a  clear  liquid,  which  maj  be  vaporized 
without  change  of  color  or  composition.  If  the  vapors  be  received 
on  a  warm  glass  slide,  they  condense  to  brilliant  crystals  of  the 
forms  illustrated  in  Plate  XV.,  fig.  3.  Crystals  may  also  be  ob- 
tained by  heating  a  small  portion  of  the  acid  in  a  reduction  tube. 

Solubility.  In  Water. — When  excess  of  the  finely-powdered  acid 
is  frequently  agitated  with  water  at  the  ordinary  temperature  for 
twenty-four  hours,  one  part  dissolves  in  2912  parts  of  the  liquid. 
Its  solubility  is  greatly  increased  by  the  presence  of  coloring  matters, 
and  also  of  the  associated  alkaloid,  even  if  only  a  trace  of  the  latter 
be  present.  It  is  much  more  soluble  in  hot  water,  from  which, 
however,  as  the  solution  cools  the  excess  soon  separates  in  delicate 
needles. 

Gelsemic  acid  is  readily  soluble  both  in  ether  and  in  chloroform. 
In  ether  of  sp.  gr.  .728,  one  part  of  the  acid  quickly  dissolves  in 
300  parts  of  the  fluid.     It  is  freely  soluble  in  alcohol. 

CHEincAX,  Reactions. — 1.  Nitric  acid. — If  a  small  portion  of 
gelsemic  acid  be  treated  with  a  drop  of  nitric  acid,  it  dissolves  with 
a  yellow  color  to  a  yellow  or  reddish  solution,  the  final  color  depend- 
ing upon  the  relative  quantity  of  the  organic  acid  present.  On 
treating  this  solution  with  excess  of  aramonia,  it  acquires  a  perma- 
nent deep  or  blood-red  color.  These  results  may  be  obtained  from 
the  1-lOOOth  of  a  grain  of  the  acid  ;  and  even  l-50,000th  grain  will 
yield,  under  the  action  of  ammonia,  a  marked  reddish  coloration. 

This  reaction,  although  exceedingly  delicate,  is  not  characteristic 
of  gelsemic  acid,  since  cesculin  yields  under  the  action  of  nitric  acid 
and  ammonia  a  similar  red  coloration.  The  distinctive  characters 
of  these  substances  will  be  pointed  out  hereafter. 

2.  Sulphuric  acid. — Sulphuric  acid  slowly  dissolves  pure  gelsemic 
acid  under  a  yellow  color  to  a  yellow  solution,  which  is  unchanged 
by  a  moderate  heat;  even  if  the  mixture  be  heated  to  100°  C.  (212° 
F.)  the  acid  is  not  decomposed.  If  the  organic  acid  is  impure,  the 
cold  sulphuric  acid  solution  may  have  a  reddish  color,  changed  to 
deep  brown  by  a  moderate  heat,  .^culin,  when  pure,  quickly  dis- 
solves in  sulphuric  acid  to  a  faintly  yellow  solution,  which  when 
moderately  heated  soon  acqunes  a  chocolate  color,  then  becomes 
charred.  If  a  small  crystal  of  potassium  dichromate  be  stirred  in  a 
sulphuric  acid  solution  of  gelsemic  acid,  green  oxide  of  chromium 
quickly  appears. 


CHEMICAL    PliOrEUTIES.  693 

3.  Sufplinric  acid  and  Ammonia. — If  a  drop  of  aqueous  am- 
monia be  allowed  to  flow  into  a  droj)  of  a  sidphurio  acid  solution 
of  gelsemic  acid,  the  latter  immediately  separates  as  a  mass  of  crys- 
talline needles,  along  the  margin  of  contact  of  the  two  liquids. 
1-lOOOth  of  a  grain  of  the  acid,  under  these  conditions,  will  yield 
a  very  copious  crystalline  deposit,  Plate.  XV.,  fig.  4.  And  even 
l-10,000th  of  a  grain,  if  only  a  minute  drop  of  the  mineral  acid 
be  employed  and  excess  of  ammonia  be  avoided,  will  yield  perfectly 
satisfactory  results.  These  crystals  may  be  repeatedly  re-examined, 
even  when  only  in  minute  quantity  and  after  long  periods,  by  treat- 
ing the  dry  residue,  after  spontaneous  evaporation,  with  a  drop  of 
water,  which  -will  readily  dissolve  the  ammonium  sulphate  present, 
whilst  the  gelsemic  acid  crystals  will  remain. 

This  is  one  of  the  most  delicate  and  characteristic  reactions  of 
gelsemic  acid  yet  known,  and  it  is  not  readily  interfered  with  by  the 
presence  of  foreign  matter.     JEsculin  fails  to  respond  to  this  test. 

4.  Hydrochloric  acid  fails  to  dissolve  or  act  upon  gelsemic  acid, 
even  when  heated  to  100°  C.  (212°  F.).  iEsculin  is  readily  soluble 
in  this  acid. 

5.  Ammonia,  and  the  fixed  caustic  alkalies,  cause  gelsemic  acid 
to  assume  an  intense  yellow  color,  and  quickly  dissolve  it  to  solutions 
having  very  striking  fluorescent  properties,  even  when  greatly  diluted. 
When  the  diluted  solution  is  examined  by  transmitted  light,  it  has 
a  yellow  color ;  under  reflected  light,  a  deep  bluish  appearance ;  and 
under  condensed  sunlight,  an  intense  blue  color  along  the  path 
of  the  condensed  rays.  This  fluorescence  still  manifests  itself  in 
solutions  containing  only  l-100,000th  of  the  acid.  It  may  also  be 
observed,  on  addition  of  an  alkali,  in  the  commercial  preparations  of 
gelsemium.  The  fluorescence  of  gelsemic  acid  is  quickly  destroyed 
by  free  acids. 

In  regard  to  the  fluorescent  properties  of  gelsemic  acid,  it  must 
be  borne  in  mind  that  cesculin  and  certain  other  vegetable  principles 
possess  similar  properties.  The  well-known  fluorescence  of  quinine 
reveals  itself  only  in  the  presence  of  a  free  acid,  being  quickly 
destroyed  by  an  alkali. 

Solutions  of  Gelsemic  Acid. — In  the  presence  of  a  free 
alkali,  gelsemic  acid  is  freely  soluble  in  water,  forming  the  fluores- 
cent solutions  just  mentioned.  From  solutions  in  ammonia,  when 
not  too  dilute,  hydrochloric  acid  precipitates  the  acid  in  its  crystalline 


694  GELSEMINE. 

state,  usually  as  delicate  needles.  In  the  presence  of  a  fixed  alkali, 
the  acid  is  precipitated  only  from  quite  strong  solutions. 

If  a  drop  of  the  amraoniacal  solution  be  allowed  to  evaporate 
spontaneously,  the  acid  is  left  in  its  free  state,  as  prisms  and  needles. 
Crystals  may  thus  be  obtained  from  a  drop  of  a  l-10,000th  solution 
of  the  acid.  The  residue  from  a  solution  of  the  acid  in  a.  fixed  alkali 
has  a  greenish-yellow  color  and  is  amorphous. 

Solutions  of  the  acid,  prepared  by  the  aid  of  just  sufficient  al- 
kali, yield  precipitates  with  solutions  of  most  of  the  metals.  In 
some  instances  these  precipitates  are  definite  compounds  of  the  acid 
and  metal ;  in  others  they  are  mixtures  of  the  metallic  oxide  and 
free  gelsemic  acid ;  whilst  in  still  others  they  are  due  to  the  reducing 
action  of  the  acid. 

1.  Acetate  of  lead  throws  down  from  a  1-1 00th  solution  of 
gelsemic  acid  a  dense,  dirty-yellow,  amorphous  precipitate,  which 
is  readily  soluble  in  acetic  acid,  but  is  soon  replaced  by  delicate 
crystalline  needles.  A  1-1 000th  solution  yields  a  very  decided  pre- 
cipitate. 

2.  Mercuric  chloride,  or  corrosive  sublimate,  produces  with  a 
1-lOOth  Solution  a  copious,  yellowish- white  precipitate,  from  which 
the  free  acid  quickly  separates  as  tufts  of  crystals.  Crystals  may 
thus  readily  be  obtained  from  even  a  drop  of  a  1-lOOOth  solution 
of  the  acid. 

3.  Silver  nitrate  causes  a  brownish -yellow  deposit,  which  soon 
darkens  in  color  and  finally  becomes  bluish-black,  due  to  the  reduc- 
tion of  the  silver  salt.  Even  a  drop  of  a  l-50,000th  solution  of  the 
acid  after  a  time  acquires  a  distinct  purplish  color. 

4.  Copper  sulphate  throws  down  from  tolerably  strong  solutions 
of  the  acid  a  dii'ty-brown  precipitate,  which  soon  acquires  a  dull  red 
color;  after  a  time  crystals  of  the  free  acid  separate. 

5.  Auric  chloride  occasions  with  strong  solutions  a  deep  blue 
deposit,  which  soon  assumes  a  green  color. 

None  of  the  above  liquid  reactions  when  taken  alone  is  charac- 
teristic of  gelsemic  acid.  In  cases,  however,  in  which  the  acid  sepa- 
rates in  the  crystalline  state,  its  true  nature  may  be  determined  by 
some  of  the  preceding  tests. 

II.  Gelsemixe. — In  its  pure  state,  gelsemine  is  a  colorless,  odor- 
less, difficultly  crystallizable  solid,  having  a  persistent  bitter  taste. 


CHEMICAL    PROPERTIES.  G95 

It  lias  a  strong  alkaline  reaction,  and  eoinj)lot(;ly  neutralizes  acids, 
forming;  sa/fs,  most  of  which  are  readily  soluble  in  water  and  in  alco- 
hol. The  hydrochloride  rather  readily  crystallizes  in  groups  of 
])risins,  Plate  XV.,  fig.  1.  The  snlphale,  nitrate,  and  hydrohroniide 
may  also  he  obtained  in  the  crystalline  form. 

When  heated,  gelsemine  fuses,  according  to  Dr.  Gerrard,  at  45° 
C.  (113°  F.),  to  a  colorless,  viscid  liquid,  which  on  cooling  solidifies 
to  a  transparent,  vitreous  mass.  At  a  higher  temperature,  the  alka- 
loid is  dissipated  without  residue,  in  the  form  of  white  fumes,  from 
which  we  failed  to  obtain  crystals. 

Solubiliti/. — In  its  free  state,  gelsemine  requires,  at  the  ordinary 
temperature,  644  parts  of  water  for  solution,  even  when  excess  of  the 
alkaloid  is  kept  in  contact  with  the  fluid  for  many  hours. 

Gelsemine  is  freely  soluble  in  chloroform  and  in  ether:  one  part 
of  the  alkaloid  is  quickly  dissolved  by  twenty-five  parts  of  the  latter 
liquid.     It  is  also  readily  soluble  in  alcohol. 

Reactions  in  the  Solid  State. — 1.  Sulphuric  acid. — When  a 
small  portion  of  pure  gelsemine  is  treated  with  a  drop  of  sulphuric 
acid,  it  slowly  dissolves,  with  little  or  no  change  of  color,  even  when 
the  solution  is  moderately  heated.  AVhen,  however,  the  alkaloid  is 
not  perfectly  pure,  it  dissolves  with  a  more  or  less  reddish  or  brown- 
ish color  to  a  solution  which  after  a  time  assumes  a  pinkish  hue,  and 
which  when  heated  acquires  a  purple  or  chocolate  color. 

If  a  minute  portion  of  powdered  potassium  dichromate  be  slowly 
stirred  in  a  sulphuric  acid  solution  of  gelsemine,  or  of  any  of  its 
colorless  salts,  a  beautiful  reddish-purple  or  cherry-red  color  manifests 
itself,  and  the  liquid  quickly  acquires  a  bluish-green  or  blue  color. 
If  only  minute  quantities  of  the  acid  and  powder  be  employed,  the 
l-10,000th  of  a  grain  of  the  alkaloid  will  yield  satisfactory  results ; 
and  even  the  l-100,000th  of  a  grain  may  develop,  at  least,  the 
reddish-purple  coloration. 

If,  in  this  test,  the  dichromate  of  potassium  be  replaced  by  eerie 
oxide,  manganic  oxide,  or  potassium  ferricyanide,  similar  results  may 
be  obtained.  If  the  sulphuric  acid  solution  of  the  alkaloid  be  heated 
on  a  water-bath  for  some  minutes,  it  no  longer  responds  to  the  color 
reaction  of  the  oxidizing  agent ;  but  the  alkaloid  is  not  destroyed, 
since  it  may  be  recovered  by  neutralizing  the  solution  with  barium 
hydrate  and  extraction  with  ether. 

This  color  reaction  of  gelsemine  resembles  somewhat  that  pro- 


696  GELSEMINB. 

duced  by  strychnine,  especially  as  obtained  from  very  minute  portions 
of  the  latter  alkaloid.  When,  however,  the  strychnine  reaction  is 
well  marked,  the  primary  blue  and  rapid  succession  of  colors  readily 
distinguish  it  from  gelsemine, 

2.  Nitric  acid. — This  acid  dissolves  perfectly  pure  gelsemine, 
and  any  of  its  colorless  salts,  with  little  or  no  color ;  but  on  spon- 
taneous evaporation  of  the  liquid,  a  permanent  bluish-green  stain 
is  left  on  the  porcelain,  even  if  only  a  minute  trace  of  the  alkaloid 
be  present.  In  the  state  in  which  gelsemine  is  usually  obtained, 
especially  as  an  ether  or  chloroform  residue,  nitric  acid  causes  it  to 
assume  a  yellowish  or  brownish-green  color,  which  quickly  changes 
to  deep  green.  About  the  least  visible  quantity  of  the  alkaloid,  if 
quietly  touched  with  a  minute  drop  of  the  acid,  may  develop  this 
green  coloration  in  a  marked  degree. 

Strychnine  and  the  other  alkaloids  fail  to  yield  a  bluish-green  or 
green  coloration  under  the  action  of  this  acid.  If  the  nitric  acid 
residue  from  gelsemine  be  treated  with  a  minute  quantity  of  sulphuric 
acid  and  potassium  dichromate,  the  reddish-purple  coloration  of  the 
alkaloid  will  be  developed.  The  nitric  and  sulphuric  acid  tests  may 
thus  be  applied  to  the  same  portion  of  the  alkaloid. 

Hydrochloric  acid  readily  dissolves  gelsemine,  if  pure,  to  a  color- 
less solution. 

The  caustic  alkalies  have  little  or  no  action  upon  the  solid  alkaloid. 

Solutions  of  Gelsemine, — Solutions  of  the  salts  of  gelsemine, 
when  pure,  are  colorless,  and  have  a  bitter  taste,  which  is  still  well 
marked  in  a  drop  of  a  1-1 000th  solution  of  the  alkaloid.  On  spon- 
taneous evaporation  of  a  drop  of  the  hydrochloride  solution,  the  salt 
may  be  left  in  its  crystalline  state. 

1.  Ammonia  and  the  fixed  alkalies  precipitate  gelsemine  from 
tolerably  strong  solutions  of  its  salts  as  a  white,  amorphous  deposit, 
which  after  a  time  becomes  more  or  less  changed  into  minute  gran- 
ules and  crystalline  plates.  The  precipitate  is  somewhat  soluble  in 
excess  of  the  precipitant.  A  drop  of  a  1-1 00th  solution  of  the  alka- 
loid yields  a  copious  precipitate.  If  a  strong  solution  be  exposed 
to  the  vapor  of  ammonia,  an  immediate  cloudiness  is  produced, 
followed  by  a  granular  deposit.  In  the  residue  from  an  aqueous 
mixture  of  a  salt  of  gelsemine  and  excess  of  ammonia,  as  already 
stated,  the  alkaloid  remains  as  a  salt,  the  ammonia  being  displaced. 

2.  Picric  acid  produces  in  solutions  of  gelsemine  salts  a  yellow, 


CHEMICAL   rnOl-EUTIES.  ('>U7 

iiraorphtnis  i)rccii)itate.  1-lOOtli  of  a  grain  of  the  alkaloid  in  one 
grain  of  water  yields  a  very  copions,  bright  yellow  (le|)osit;  l-lOOOtli 
grain,  a  greenish -yellow  precipitate. 

3.  Iodine  in  a  solution  of  potassluin  iodide  throws  down  from 
solutions  of  salts  of  gelseniine  a  brown,  amorphous  precipitate 
which  is  only  sparingly  soluble  in  acetic  acid.  The  precipitate  still 
appears  in  a  drop  of  a  l-10,000tli  solution  of  the  alkaloid. 

4.  Bromine  in  bromohydric  acid  causes  a  yellowish,  amorphous 
precipitate,  which  still  manifests  itself  in  a  l-5000th  solution  of  the 
alkaloid. 

5.  Auric  chloride  produces  a  yellow  precipitate,  which  dissolves 
with  difficulty  in  acetic  acid.  A  few  drops  of  a  1-lOOOth  solution 
of  a  salt  of  the  alkaloid  yield  a  very  marked  precipitate,  which 
quickly  dissolves  on  heating  the  mixture  and  separates  in  the  gran- 
ular form  as  it  cools.  According  to  A.  Gerrard,  the  ])recipitate  has 
the  composition  2Ci2Hi,N02;  HCl,2AuCl3. 

6.  P/afinic  chloride  occasions  in  tolerably  strons  solutions  of 
gelsemine  salts  a  light  yelloAV  precipitate,  which  becomes  partly 
granular  and  is  readily  soluble  on  heating  the  mixture.  Its  com- 
position is  2Ci2Hi,N02;HCl,PtCl^  (Gerrard). 

7.  Mercuric  chloride  throws  down  from  strong;  solutions  of  the 
salts  of  the  alkaloid  a  white  precipitate,  which  is  only  sparingly 
soluble  in  hydrochloric  acid.  Comparatively  large  granules  may 
sometimes  be  obtained  from  the  precipitate. 

8.  Potassium  dichromate  produces  in  a  1-lOOth  solution  of  a 
gelsemine  salt  a  copious,  yellow  precipitate,  Avhich  becomes  somewhat 
granular.  Solutions  but  little  more  dilute  fail  to  yield  a  precipitate. 
Sulphuric  acid  causes  the  precipitate  to  assume  a  deep  bluish-green 
color,  and  on  stirring  the  mixture  the  characteristic  purple  coloration 
of  the  alkaloid  is  developed.  If  excess  of  the  dichromate  reagent 
be  avoided  and  the  liquid  evaporated  spontaneously,  the  residue 
from  even  the  l-10,000th  of  a  grain  of  gelsemine  will,  when  treated 
with  sulphuric  acid,  yield  a  series  of  purple  colorations  followed  by 
a  bluish-o;reen  hue. 

Similar  color  results  may  be  obtained  with  sulphuric  acid  by 
employing  potassium  ferrieyanide  as  the  precipitant.  This  reagent, 
however,  produces  precipitates  from  only  concentrated  solutions  of 
gelsemine  salts. 

It  need  hardly  be  stated  that  none  of  the  foregoing  liquid  reac- 


698  GELSEMINE,   AND   GELSEMIC  ACID. 

tions  is  in  itself  characteristic  of  gelsemine.  But  if  the  precipitates 
produced  by  any  of  the  reagents  be  treated  with  concentrated  sul- 
phuric acid  and  potassium  dichromate,  or  other  color-developing 
agent,  the  peculiar  purple  coloration  of  gelsemine  will  be  developed. 
It  must  be  remembered,  however,  that  the  color  reaction  of  some  of 
these  precipitates,  especially  when  excess  of  the  precipitant  is  present, 
is  not  so  delicate  as  that  of  the  free  alkaloid  or  its  pure  salts. 

Recovery  from  Organic  Mixtures. 

Suspected  Solutions  and  Contents  of  the  STOMAcn. — 
The  mixture,  diluted  with  water  if  necessary,  is  slightly  acidulated 
with  acetic  or  hydrochloric  acid,  and  digested  at  a  moderate  heat  on 
a  water-bath  for  an  hour  or  longer.  The  cooled  liquid  is  strained 
through  muslin,  the  solids  washed  with  alcohol,  and  the  united  fluids 
concentrated  to  one  or  two  fluid-ounces  (30  to  60  c.c),  or  even  less 
if  only  a  small  portion  of  solid  matter  is  present.  The  liquid  is 
now  filtered,  and  any  solids  on  the  filter  washed  with  a  mixture  of 
equal  parts  of  alcohol  and  water.  It  is  again  concentrated,  taking 
care  to  expel  the  alcohol,  allowed  to  cool,  and,  if  solid  matter  sepa- 
rates, again  filtered.    The  analysis  now  divides  itself  into  two  parts. 

a.  Gelsemic  acid. — The  liquid,  having  still  an  acid  reaction,  is 
agitated  with  about  twice  its  volume  of  pure  ether,  which  will  take 
up  any  gelsemic  acid  present  and  become  more  or  less  fluorescent. 
After  decanting  the  ether,  the  aqueous  liquid  is  washed  once  or 
twice  with  small  portions  of  fresh  ether,  which  is  collected  with 
that  first  employed.  The  aqueous  liquid  is  reserved  for  examina- 
tion for  the  alkaloid. 

The  ether  thus  employed  is  allowed  to  evaporate  spontaneously, 
small  portions  at  a  time,  in  a  thin  glass  capsule.  The  gelsemic  acid 
may  now  be  found,  especially  in  the  margin  of  the  deposit,  in  the 
form  of  groups  or  single  needles,  readily  seen  by  a  low  power  of 
the  microscope.  Any  crystals  thus  obtained  may  be  collected,  and, 
if  not  in  too  minute  quantity,  washed  with  a  few  drops  of  absolute 
alcohol,  then  examined  by  the  appropriate  tests  for  the  acid. 

If  much  foreign  matter  is  still  present,  the  entire  residue  may  be 
treated  with  a  little  water  containing  a  drop  of  ammonia,  and  the 
liquid,  if  necessary,  filtered.  After  examining  the  alkaline  liquid 
in  regard  to  its  fluorescence,  it  is  slightly  acidulated  with  acetic  acid 
and  extracted  with  ether,  which  is  allowed  to  evaporate  spontane- 


RECOVERY    FROM   TIIK   TISSUES. 


699 


ously.  A  portion  of  tlic  ether  residue  may  he  examined  hy  the 
nitric  acid  and  ammonia  test  for  tlie  organic  acnd.  Another  portion 
may  be  dissolved  in  a  small  dro])  of  sulphuric  acid,  and  then  a 
minute  drop  of  ammonia  carefully  added,  when  any  gelsemic  acid 
present  will  separate  as  very  delicate  needles.  Both  these  tests  may 
react  with  the  gelsemic  acid  even  in  the  presence  of  considerable 


foreiern  matter 


b.  Gelsemine.— The  acid  aqueous  liquid  from  which  the  gelsemic 
acid  was  extracted  by  ether  is  gently  warmed  until  the  dissolved 
ether  has  been  expelled.  It  is  then  rendered  slightly  alkaline  by 
ammonia  or  sodium  carbonate,  and  any  gelsemine  present  extracted 
by  ether  or  chloroform  in  the  usual  manner. 

Should  the  ether  or  chloroform  residue  be  too  impure  for  the 
satisfactory  application  of  the  tests,  it  is  treated  with  a  small  quan- 
tity of  water  slightly  acidulated  with  hydrochloric  acid,  and  the 
filtered  solution,  rendered  alkaline,  again  extracted  with  ether. 
Portions  of  the  final  residue  should  be  examined  by  the  sulphuric 
acid  and  potassium  dichromate  and  the  nitric  acid  tests  for  the 
alkaloid.  It  may  be  remarked  that  the  reactions  of  these  tests  are 
more  readily  interfered  with  by  the  presence  of  foreign  matter  than 
those  of  the  corresponding  tests  for  gelsemic  acid. 

After  the  above  general  method,  we  have  in,  several  instances 
obtained  very  satisfactory  evidence  of  the  presence  of  both  gelsemic 
acid  and  gelsemine  in  the  stomach-contents  of  animals  poisoned  by 
small  doses  of  gelsemium  preparations.  So,  also,  in  the  case  already 
cited,  in  which  three  teaspoonfuls  of  the  fluid  extract  proved  fatal  to 
a  woman,  very  satisfactory  evidence  of  the  presence  of  the  organic 
acid,  and  of  the  alkaloid  in  minute  quantity,  was  obtained  from  the 
contents  of  the  stomach  four  and  a  half  months  after  death. 

From  the  Tissues.— In  gelsemium  poisoning  both  gelsemic 
acid  and  gelsemine  are  absorbed,  and  enter  the  circulation  in  appar- 
ently the  relative  proportions  in  which  they  are  present  in  the  plant. 
The  absorbed  poison  may  be  recovered  from  the  liver  by  treating  the 
finely-divided  or  crushed  tissue  wnth  several  times  its  weight  of 
water  slightly  acidulated  with  hydrochloric  acid,  and  gently  warm- 
ing the  mixture  on  a  water-bath  for  some  hours,  occasionally  adding 
w^ater  to  replace  that  evaporated.  The  cooled  liquid  is  strained  and 
the  solids  well  washed  with  water.  The  clear  liquid  is  concentrated 
at  a  moderate  heat  to  a  small  volume,  and,  when  cooled,  filtered. 


700  GELSEMINE,   AND   GELSEMIC  ACID. 

Any  gelsemic  acid  present  is  now  extracted  from  the  still  acid 
solution  by  ether  in  the  manner  already  indicated ;  after  which,  the 
dissolved  ether  being  expelled,  the  aqueous  liquid  is  rendered  slightly 
alkaline  and  the  alkaloid  extracted  in  a  similar  manner. 

A  cat  which  had  been  under  the  influence  of  the  drug  for  fifteen 
hours  was  given  two  drachms  of  the  fluid  extract.  The  animal 
was  immediately  paralyzed,  and  was  dead  fifteen  minutes  later. 
The  liver,  on  being  examined  after  the  above  method,  furnished 
groups  of  crystals  of  gelsemic  acid,  and  very  satisfactory  evidence 
of  the  presence  of  gelsemine.  Like  satisfactory  results  were  ob- 
tained from  the  liver  of  a  rabbit  killed  by  the  drug. 

Feom  the  Blood. — A  few  ounces  of  the  blood  are  mixed  with 
about  five  volumes  of  a  mixture  of  equal  parts  of  alcohol  and  water, 
a  few  drops  of  acetic  or  hydrochloric  acid  added,  and  the  whole  agi- 
tated in  a  bottle  until  a  homogeneous  mixture  is  formed.  This  is 
moderately  heated  in  the  closed  bottle  for  some  time  in  a  water-bath, 
the  mixture  being  frequently  agitated.  The  cooled  liquid  is  strained, 
and  the  solids  washed  with  diluted  alcohol  and  pressed.  It  is  then 
concentrated  at  a  moderate  heat,  filtered,  and  the  filtrate  evaporated 
to  a  thin  syrup ;  this  is  extracted  with  water  and  the  filtered  liquid 
concentrated  to  a  small  volume. 

From  the  liquid  thus  prepared  the  gelsemic  acid  and  gelsemine 
are  extracted  by  ether  in  the  usual  manner. 

A  fluid-ounce  of  blood  taken  from  the  cat  mentioned  above  was 
examined  after  this  method.  The  ether  extract  from  the  acid  aqueous 
liquid  presented  a  well-marked  fluorescence,  and  on  evaporation  left 
tufts  of  crystalline  needles  of  gelsemic  acid ;  and  a  portion  of  the 
residue  gave  a  deep  red  coloration  with  nitric  acid  and  ammonia; 
whilst  another  portion,  when  treated  with  sulphuric  acid  and  ammo- 
nia, gave  a  good  deposit  of  crystalline  needles.  So,  also,  the  ether 
extract  from  the  alkaline  liquid  furnished  very  satisfactory  evidence 
of  the  presence  of  gelsemine. 


APPENDIX. 


BLOOD. 

* 

COMPOSITION— DETECTION-DISCRIMINATION. 

I.   General  Nature  and  Properties  of  Blood. 

Physical  Characters.— In  its  natural  condition,  the  blood  is 
a  somewhat  viscid,  opaque  liquid,  of  a  characteristic  red  color,  which 
is  bright  scarlet  in  arterial  and  of  a  purplish  or  brownish  hue  in 
venous  blood.  On  exposure  to  the  air  the  blood  of  the  veins  acquires 
the  florid  hue  of  that  of  the  arteries.  The  blood  -has  a  feebly  alka- 
line reaction,  a  saline  taste,  and,  while  still  warm,  a  faint  odor,  which 
differs  somewhat  in  the  blood  of  different  animals.  Its  average 
specific  gravity  in  man  is  about  1055,  ranging  from  1045  to  1075, 
and  being  slightly  lower  in  women  than  in  men,  and  still  lower  in 
children.  The  specific  gravity  of  the  blood  of  domestic  animals  is 
about  the  same  as  that  of  man. 

Composition. — When  examined  under  the  microscope,  the  blood 
is  found  to  consist  of  a  transparent,  colorless,  or  very  faintly  yellow 
liquid,  known  as  the  liquor  sanguinis,  or  plasma,  in  which  is  sus- 
pended a  great  number  of  very  minute  solid  bodies  known  as  the 
blood-corpuscles. 

The  liquor  sanguinis  consists  chiefly  of  water  holding  in  solution 
albumen,  fibrin,  extractive  matters,  and  certain  inorganic  salts,  of  which 
the  principal  are  sodium  chloride  and  carbonate.  The  corpuscles  are 
of  two  kinds  :  the  colored,  consisting  largely  of  the  red  coloring  sub- 
stance, variously  termed  hcemoglobin,  hcematoglobidin,  and  hcenudocrys- 
tallin,  which  confers  upon  the  blood  its  red  color ;  and  the  colorless 

701 


702  BLOOD. 

or  white  corpuscles,  these  being  destitute  of  color  and  present  only  in 
small  proportion  to  the  former. 

These  several  components  exist  in  about  the  following  proportions 
in  1000  parts  of  human  blood  :  water,  790 ;  albumen,  65 ;  fibrin,  3  ; 
extractive  matters  and  salts,  17 ;  corpuscles  (dry),  125  parts.  In 
their  moist  state,  it  is  estimated  that  the  corpuscles  form  about  one- 
half  the  volume  of  the  blood.  The  specifi^c  gravity  of  the  red  cor- 
puscles, according  to  C  Schmidt,  is  about  1088,  and  that  of  the  fluid 
in  which  they  float  about  1028.  When  seen  singly,  the  red  corpuscles 
have  a  pale  reddish-yellow  hue. 

Coagulation. — Soon  after  being  drawn  from  the  body,  the  blood 
undergoes  spontaneous  coagulation,  whereby  it  finally  separates  into 
two  distinct  portions,  namely,  the  crassamentum,  or  clot,  consisting 
of  the  fidrin  with  the  corpuscles  entangled  in  its  meshes ;  and  the 
serum,  holding  in  solution  the  albumen  and  saline  matters.  Tliis 
process  usually  begins  in  normal  human  blood,  when  exposed  to  the 
air,  in  from  two  to  three  minutes,  and  in  about  eight  minutes  the 
mass  forms  a  jelly.  It  is,  however,  subject  to  considerable  variation, 
and  also  varies  in  the  blood  of  different  animals. 

According  to  Hewson,  coagulation  may  take  place  within  a  few 
seconds,  whilst  it  may  be  delayed  for  an  hour  or  longer.  (Op.  cit., 
72.)  As  is  well  known,  the  process  is  much  influenced  by  vari- 
ous conditions  and  agents.  Thus,  an  increased  temperature  hastens, 
while  a  diminished  temperature  delays,  coagulation.  So,  also,  the 
addition  of  water  up  to  four-tenths  the  volume  of  blood  hastens, 
and  a  larger  proportion  retards,  the  process  (Hasebrock,  1883).  In 
like  manner  a  minute  quantity  of  sodium  chloride  hastens,  and  a 
large  quantity  prevents,  coagulation. 

Corpuscles. — The  existence  of  the  blood-corpuscles  was  first 
announced  by  Malpighi,  in  1661,  he  having  observed  them  in  the 
blood  of  the  hedgehog.  They  were  first  seen  in  human  blood  by 
Leeuwenhoek,  in  1664,  and  he  observed  that  the  red  color  of  tiie 
blood  resided  in  the  corpuscles,  and,  as  in  man,  they  were  circular 
in  outline  in  the  blood  of  the  rabbit,  ox,  and  sheep,  but  oval  in 
birds,  fish,  and  the  frog.  ( Wattes  Diet.  Chem.,  i.  604.)  Swammer- 
dam  was  the  first  to  observe  the  blood-corpuscles  of  the  frog.  The 
earlier  observers  believed  the  corpuscles  to  be  globular  in  form,  but 
Senac,  in  1749,  announced  that  they  were  all  more  or  less  flattened. 

Number. — According  to  Vierordt,  and  also  Welcker,  one  cubic 


GENERAL   NATURE   AND   PROPERTIES.  703 

railHmetre  (about  l-25th  incli  linear)  oi"  iiortnal  Iminan  Mood  con- 
tains about  5,000,000  rod  (u)rpus(!lc,s.  According  to  these  estimates, 
which  have  been  confirmed  by  more  recent  observers,  a  single  grain 
of  human  blood  contains  about  325,000,000  corpuscles.  The  weight 
of  a  single  corpuscle  may  be  stated  approximately  at  l-800,000,000th 
of  a  grain,  or,  according  to  Harting,  at  1-13,1 14,000th  of  a  niilli- 
granune. 

The  number  of  red  corpuscles  is  something  less  in  the  blood  of 
women  than  in  that  of  men,  and  also  in  arterial  than  in  venous 
blood,  and  it  even  varies  in  different  parts  of  tiie  same  circula- 
tion. It  also  varies  in  the  blood  of  different  animals,  even  of  the 
same  class.  Thus,  in  the  rabbit  there  are  about  3,500,000  corpuscles 
and  in  the  goat  about  18,000,000  per  cubic  millimetre.  In  general, 
birds  have  usually  more  than  mammalia,  and  cold-blooded  far  less 
than  warm-blooded  animals. 

Forms  of  the  Corpuscles. — The  red  corpuscles  of  the  blood 
of  all  vertebrate  animals  present  one  or  other  of  two  forms,  being 
either  circular  in  outline  or  more  or  less  oval.  In  all  mammalia,  ex- 
cept in  embryo,  the  corpuscles  are  destitute  of  a  nucleus,  while  in 
all  oviparous  animals  they  contain  a  nucleus.  Hence  the  former 
class  was  designated  by  Prof.  Gulliver,  who  first  pointed  out  the  dis- 
tinction, the  Apyrenctimatous  ;  and  the  latter  group,  including  Birds, 
Reptiles,  and  Fishes,  the  Pyrencematous  Vertebrates. 

1.  Non-nucleated  Corpuscles. — In  man  and  all  mammalia,  except 
the  camel  tribe,  the  red  corpuscles  are  circular,  flattened,  biconcave 
disks,  which  have  been  aptly  compared  to 
double  concave  lenses  with  rounded  edges. 
As  seen  under  the  microscope,  the  free  cor- 
puscles almost  invariably  present  the  flat  sur- 
face to  view.  Fig.  13.  The  thickness  of  the 
corpuscle  at  its  edge  is  usually  between  one-        blood-coepuscles.— i.  Mam- 

-  11        T  n    1        T   1  malian :    a,  front  view ;    6,  on 

third  and  one-fourth  the  diameter  of  the  disk.     edge.      2.  Oviparous;    front 

In  the  camel  tribe,  the  corpuscles  have     ^'""■'  '^°'"'''s  °"'=^^"^- 
an   oval  or   elliptical   outline,  and   the   sides   are   slightly  convex. 
The  corpuscles  of  this  tribe,  however,  conform  to  those  of  mammalia 
in  general,  in  being  destitute  of  a  nucleus,  and  in  smallness  of  size. 

In  size  the  red  corpuscles  of  the  mammalia  differ  more  or  less  in 
the  different  members  of  the  class;  and  they  also  vary  somewhat  in 
the  blood  of  the  same  animal.     But,  as  we  shall  see  hereafter,  verv 


704  BLOOD. 

close  uniformity  exists  in  much  the  greater  proportion  of  the  red 
corpuscles  of  the  same  animal.  With  only  few  exceptions,  the 
average  diameter  of  the  red  corpuscles  of  mammalian  animals 
varies  from  l-3000th  to  l-6000th  of  an  inch,  or  through  a  range  of 
l-6000th  of  an  inch.  The  largest  corpuscles  of  this  kind  are  those 
of  the  elephant,  having  a  mean  diameter  of  about  l-2750th  of  an 
inch,  and  the  smallest  are  found  in  the  musk-deer,  these  measuring 
about  l-12,325th  of  an  inch,  the  extreme  range  being,  therefore, 
about  l-3500th  of  an  inch  ;  that  is,  the  diameter  of  the  largest  mam- 
malian blood-corpuscles  known  is  about  l-3500th  of  an  inch  greater 
than  that  of  the  smallest  known. 

In  regai'd  to  the  structure  of  the  red  corpuscles,  histologists  have 
held  very  different  views.  By  many  of  the  older  writers  they  were 
regarded  as  composed  of  a  distinct  cell-wall  or  membrane,  filled 
with  a  fluid  containing  the  red  coloring  matter  of  the  blood.  But 
according  to  more  recent  observers  they  consist  of  a  colorless,  highly 
elastic,  porous  or  cavernous  mass,  or  "  stroma,"  albuminous  in  sub- 
stance, and  the  interstices  of  which  are  filled  by  the  coloring  matter 
of  the  corpuscle. 

2.  Nucleated  Corpuscles. — In  the  blood  of  all  birds,  reptiles,  and 
fishes  the  red  corpuscles  contain  a  distinct  nucleus,  which  is  generally 
oval  in  form,  but  sometimes  nearly  or  altogether  circular.  The 
nucleus  is  dark  in  color,  rough  in  contour,  and  usually  occupies  the 
central  portion  of  the  corpuscle,  but  sometimes  it  is  eccentric.  In 
the  blood  of  birds  the  nucleus  is  relatively  much  more  elongated  than 
the  corpuscle  itself;  in  reptiles  and  fishes  it  has  usually  the  figure  of 
the  corpuscle. 

The  corpuscles  in  all  these  classes,  except  in  a  small  family  of 
fishes  (the  Cyclostomata),  are  more  or  less  oval  in  form,  the  ellipticity 
being  greatest  in  the  blood  of  birds,  in  which  the  long  diameter  of 
the  disk  may  be,  according  to  Gulliver,  twice  its  short  diameter. 
This  difference  is  somewhat  less  in  the  blood  of  reptiles  and  least 
in  that  of  fishes,  in  which  the  corpuscles  pass  by  gradations  to  the 
circular  form. 

In  size  the  corpuscles  of  these  classes  are  considerably  larger 
than  in  the  mammalia,  the  largest  being  found  in  the  blood  of 
reptiles,  especially  batrachians.  In  the  blood  of  the  AmpMumia 
tridactylum  the  corpuscles  can  be  seen  by  the  unaided  eye,  their 
length  being  about  l-350th  of  an  inch. 


GENERAL  NATURE  AND  PROPERTIES.  705 

The  flattened  sides  of  the  nucleated  corpuscles  are  generally 
niDre  or  less  convex,  and  the  thickness  of  the  disks  is  about  one- 
third  their  short  diameter. 

In  the  Cyclostomata,  the  lowest  order  of  fishes,  the  corpuscles  are 
circular  in  form,  flattened,  and  have  their  sides  slightly  concave; 
hence  they  differ  from  those  of  man  and  the  regular  mammalia 
only  in  the  presence  of  a  nucleus  and  in  larger  size  (l-2100th  of  an 
inch).  In  the  Amphioxus  lanceolatm,  a  member  of  this  order  and 
the  very  lowest  of  vertebrates,  there  is  an  entire  absence  of  the  red 
corpuscles,  the  circulating  fluid  containing  only  colorless  disks. 

Action  of  Water  and  Reagents  on  Red  Corpuscles. — 
The  red  corpuscles  of  the  blood  of  all  animals  are  more. or  less 
affected  by  most  liquids  and  certain  gases. 

1.  Circular  Corpuscles. —  Water,  if  added  only  in  very  minute 
quantity  to  the  blood  of  man  or  any  of  the  regular  mammalia, 
causes  the  corpuscles  to  become  thicker  and  somewhat  cUrainished  in 
diameter,  the  concave  sides  becoming  first  flat,  then  convex,  the 
thickening,  according  to  Frey,  beginning  in  the  margins.  After  a 
time,  or  if  more  water  be  added,  the  corpuscles  still  increase  in 
thickness,  become  less  in  diameter,  pale  in  color,  and  finally  entirely 
decolorized  and  spherical  in  form,  the  diameter  being  reduced  in 
human  blood-corpuscles  to  about  l-4200th  of  an  inch  or  less.  In 
this  state  they  are  so  transparent  as  to  be  nearly  or  altogether  invisi- 
ble to  the  microscope.  The  addition  of  a  potassium  iodide  solution 
tinged  with  iodine  will  render  the  outlines  more  distinct,  and  may 
render  them  quite  visible  after  they  have  disappeared  from  view. 

If  the  blood  be  treated  at  once  with  a  comparatively  large  quan- 
tity of  water,  the  corpuscles  are  instantly  deprived  of  color,  and  be- 
come globular  and  nearly  or  wholly  inv^isible,  or  they  may  undergo 
entire  disintegration.  ISTot  only  is  the  effect  of  water  thus  determined 
somewhat  by  the  relative  quantity  employed,  but  its  action  differs 
somewhat,  it  is  said,  on  the  blood  of  different  animals.  That  the 
corpuscles,  by  the  action  of  water,  are  rendered  spherical  and  less  in 
diameter  was  first  observed  by  Hewson. 

If  the  corpuscles  when  thus  distended  be  treated  with  a  neutral 
liquid  of  greater  density,  as  a  solution  of  common  salt,  they  regain 
more  or  less  their  original  forms. 

It  has  long  been  known  that  some  of  the  corpuscles  in  the  same 

45 


706  BLOOD. 

sample  of  blood  resist  the  action  of  water  very  much  more  th^n 
others,  the  former  retaining  their  color  and  form  long  after  the  latter 
have  entirely  disappeared. 

In  neutral  liquids  of  the  same  density  as  the  liquor  sanguinis, 
the  corpuscles  undergo  little  or  no  change.  In  liquids  more  dense 
than  the  serum,  they  become  shrivelled,  and  crenated  or  jagged 
in  outline.  The  caustic  alkalies  quickly  dissolve  the  corpuscles, 
ammonia  acting  more  energetically  than  the  fixed  alkalies. 

2.  Oval  Corpuscles. — The  effect  of  vKder  upon  corpuscles  of  oval 
form  is  much  the  same  as  that  upon  the  circular  disks.  The  sides 
become  more  convex,  the  long  diameter  shortens  and  the  short 
diameter  lengthens,  and  they  become  lighter  in  color.  As  the  action 
continues,  they  assume  a  nearly  or  altogether  spherical  form,  with 
a  diameter  intermediate  between  the  long  and  short  diameters  of 
the  original  corpuscle,  and  finally  become  colorless  and  exceedingly 
transparent,  or  invisible.  Thus,  under  the  action  of  water,  the  cor- 
puscles of  oviparous  animals  may  closely  resemble  in  outline  those 
of  mammalia  under  like  conditions ;  but  the  presence  of  the  nuclei 
and  their  larger  size  readily  distinguish  the  former  from  the  latter. 

Water  has  little  action  upon  the  nuclei,  other  than  to  cause  them 
to  become  more  spherical ;  they  may  frequently  be  seen  even  when  the 
outlines  of  the  corpuscles  have  become  invisible.  If  the  swollen 
corpuscles  be  treated  with  a  more  dense  liquid,  they  regain  their 
original  forms.  Acetic  acid  causes  the  corpuscles  to  thicken  and 
become  transparent,  but  it  does  not  readily  act  upon  the  nuclei. 

White  Corpuscles. — The  white  or  color^less  corpuscles,  known 
also  as  leucocytes,  were  first  described  by  Hewson.  These  have  the 
singular  property  of  amoeboid  or  spontaneous  movement,  and  of 
absorbing  within  themselves,  when  brought  in  contact,  finely -divided 
coloring  matters.  Their  average  proportion  in  normal  human  blood 
is  one  to  about  350  of  the  red  corpuscles ;  but  their  number  is 
subject  to  great  variation,  depending  upon  age,  sex,  and  various 
conditions. 

The  colorless  corpuscles  are  globular  or  spheroidal  in  form,  more 
or  less  granular,  and  contain  one  or  more  nuclei,  which  may  be 
either  round,  oval,  or  irregular  in  outline,  and  sometimes  more  or 
less  superimposed  one  upon  the  other.  The  colorless  corpuscles  have 
a  higher  refractive  power,  greater  firmness,  and  are  specifically 
lighter,  than  the  red  corpuscles.    The  nuclei  are  not  generally  visible 


GENKRAI.    NATURE    AND    PROPERTIES.  707 

until  tlio  corpiiselo  is  treated  with  acetic  acid  or  other  reagent,  which 
dissolves  or  renders  the  granules  of  the  disk  more  transparent. 

In  size  the  white  corpuscles  are  pretty  uniform  throughout  the 
entire  Vertebrata,  ranging  in  diameter  from  about  l-2500th  to 
l-3000th  of  an  inch,  and  being,  according  to  Prof.  Gulliver,  as 
large  in  the  musk-deer  as  in  ordinary  mammals.  As  is  well  known, 
the  proportion  of  the  white  to  the  red  corpuscles  is  sometimes  very 
greatly  increased  in  disease  [leucocythccmia],  in  which  the  former  may 
almost  equal  in  number  the  latter. 

Water  causes  the  colorless  corpuscles  to 'become  smoother  in 
appearance  and  more  transparent,  brings  to  view  the  nuclei,  and 
finally  causes  the  mass  to  disintegrate. 

Histologists  are  now  generally  agreed  that  the  white  corpuscles 
of  the  blood  are  identical  in  general  character  with  the  ordinary 
corpuscles  of  lymph,  chyle,  saliva,  mucus,  and  pus. 

Identification  of  Blood. 

When  in  its  fresh  condition,  the  physical  characters  of  blood  are 
usually  quite  sufficient  to  distinguish  it  from  all  other  liquids.  But 
as  presented  for  identification  in  medico-legal  investigations,  it  is 
generally  in  the  dried  state,  in  the  form  of  stains,  more  or  less  minute, 
which  may  be  recent  or  old  and  may  have  been  washed. 

Under  these  circumstances  the  presence  of  one  or  more  of  the 
constituents  of  blood  may  be  established  either  by  their  chemical 
properties,  by  their  optical  effects,  or  by  their  microscopic  appearances, 
or  by  these  methods  combined. 

In  medico-legal  practice,  when  any  account  is  given  of  a  suspected 
stain,  the  primary  question  usually  presents  itself  under  one  or  other 
of  the  following  forms :  1st.  Is  the  suspected  stain  blood  ?  2d.  Is 
it  the  blood  of  an  oviparous  animal?  3d.  Is  it,  or  may  it  be,  that 
of  a  specific  mammal,  or  may  it  be  human  blood  ?  In  many  in- 
stances, however,  no  explanation  of  this  kind  is  given  or  obtained, 
and  the  medical  jurist  has  to  determine  whether  the  stain  is  really 
blood,  and,  if  so,  its  true  character,  so  far  as  he  can. 

Physical  Character  of  Blood-stains.— The  color  and  general  ap- 
pearance of  a  blood-stain  will  de])end  much  upon  its  thickness,  age, 
the  nature  of  the  material  upon  which  deposited,  and  also  the 
condition  of  the  atmosphere  to  which  exposed.  The  characteristic 
red  color  of  a  fresh  stain  will  after  a  time  change  to  reddish-brown 


708  BLOOD. 

or  brown.  This  change  may  take  place  even  within  a  few  hours. 
When  upon  a  fabric,  dried  blood  imparts  to  it  more  or  less  stiffness. 
The  side  of  the  fabric  upon  which  the  stain  was  received  should  be 
noted,  and  also  its  exact  location  on  the  article  upon  which  found. 

For  the  examination  of  minute  stains,  a  low  power  of  the  micro- 
scope, especially  with  the  binocular  instrument,  with  condensed 
reflected  light,  may  be  employed  with  great  advantage.  If  blood, 
the  stain  will  present  a  bright  shining  appearance  and  a  highly 
characteristic  red  color.  In  this  manner  coagula  may  be  found  even 
in  exceedingly  minute  stains.  Stains  upon  dark-colored  substances 
may  sometimes,  it  is  said,  be  best  detected  by  artificial  light. 

Water  dissolves  the  hcemoglobin,  or  red  coloring  matter,  of  dried 
blood,  together  with  the  albumen  and  salts,  leaving  the  fibrin  as  a 
nearly  colorless  film.  The  red  color  of  the  solution,  even  when 
containing  the  coloring  matter  of  only  one  part  of  blood  in  1000 
parts  of  liquid,  may  be  well  marked,  especially  ou  lookiug  down  the 
tube  in  which  it  is  contained ;  a  reddish  hue  may  even  be  observed 
in  a  l-5000th  solution  of  blood. 

A  portion  of  the  stained  fabric,  or  the  matter  scraped  from  a 
spot,  is  treated  in  a  very  small  test-tube  with  a  little  pure  water, 
when,  if  the  stain  is  recent  or  comparatively  so,  the  liquid  will 
quickly  assume  a  red  color,  which  at  first  appears  as  a  red  coloration 
around  the  stain ;  but  when  the  stain  is  older,  some  hours  may  be 
required  for  its  solution,  and  the  liquid  may  acquire  only  a  brown- 
ish hue.  The  age  of  a  stain  cannot  always  be  determined  by  its 
solubility  in  water,  since  one  some  months  old  may  dissolve  more 
readily  than  another  only  a  few  weeks  old.  If  the  stain  has  been 
heated,  the  coloring  matter  will  generally  be  insoluble  in  water ;  but 
it  may  be  rendered  soluble  by  the  addition  of  a  little  alkali.  Very 
old  stains  usually  entirely  resist  the  action  of  pure  water.  Any 
stains  removed  from  a  substance  for  examination  should  be  corre- 
spondingly marked. 

Any  solution  thus  obtained  may  now  be  examined  by  the  chem- 
ical tests,  or  by  means  of  the  spectroscope,  for  blood. 

II.   Chemical  Tests  for  Blood. 

1.  Heat. — If  an  aqueous  solution  of  blood  be  heated  to  near  the 
boiling  point,  its  red  color  is  quickly  discharged,  with  the  formation 
of  a  dirty-brownish  precipitate  or  turbidity,  due  to  the  coagulation 


CHEMICAL    PROPERTIES.  709 

of  the  albumen;  tlie  upper  portion  of  the  liquid  usually  presents  a 
faint  yellow  hue.  A  1-1 000th  solution  of  blood  will  yield  only  a 
marked  turbidity  of  a  lii!;ht  color. 

U'  a  drop  of  sodium  hydrate  solution  be  now  added,  the  precipi- 
tate or  turbidity  immediately  disappears,  and  the  liquid  acquires  a 
more  or  less  red  color  by  reflected  and  a  greenish  hue  by  transmitted 
light,  being  dichroic.  The  precipitate  may  be  reproduced  by  adding 
a  drop  of  nitric  acid.  If  a  few  drops  of  the  acid  be  allowed  to  flow 
down  the  side  of  the  tube  and  quietly  subside  to  the  bottom,  a  white 
zone  will  appear  at  the  surface  of  contact  of  the  two  liquids,  even  if 
only  1-lOOOth  of  blood  be  present. 

The  immediate  discharge  of  the  red  color  of  solutions  of  blood, 
with  the  formation  of  a  coagulum,  when  heated,  distinguishes  it 
from  the  red  extracts  of  roots,  fruits,  flowers,  and  dyes,  which  are 
unchanged  by  heat. 

2.  Ammonia. — When  diluted  and  added  in  limited  quantity, 
ammonia  has  little  or  no  action  upon  the  red  color  of  solutions  of 
blood;  if  added  in  large  quantity,  the  solution  will  assume  a  brown- 
ish hue.  A  minute  quantity  of  ammonia  really  heightens  the  color 
of  a  blood  solution.  Under  the  action  of  this  reao-ent  the  red  color 
of  vegetable  extracts,  cochineal,  and  certain  mineral  substances  is 
either  changed  to  green,  violet,  crimson,  or  blue,  or  entirely  dis- 
charged, depending  upon  the  nature  of  the  coloring  matter. 

3.  G^iaiacum  Test. — On  treatino;  a  solution  of  the  colorino-  matter 
of  blood  with  an  alcoholic  tincture  of  gudiacum  and  an  ethereal  solu- 
tion of  hydrogen  peroxide,  a  deep  blue  coloration  is  produced,  due  to 
the  oxidation  of  the  guaiacura  resin.  The  alcoholic  solution  should 
be  freshly  prepared  from  inner  portions  of  the  resin.  The  ethereal 
solution  of  peroxide  of  hydrogen,  known  in  the  shops  as  ozonie  ether, 
may  be  prepared  by  suspending  some  pure  barium  dioxide  in  water, 
adding  an  equivalent  quantity  of  dilute  sulphuric  acid,  and  extract- 
ing the  liberated  hydrogen  peroxide  by  ether.  A  portion  of  the 
ether  extract,  if  fit  for  use,  will  strike  a  beautiful  blue  or  violet 
coloration  on  the  addition  of  a  fragment  of  chromic  acid. 

In  applying  this  test,  a  drop  of  the  blood  solution,  placed  over  a 
white  surface  or  in  a  porcelain  dish,  is  first  treated  with  a  drop  of 
the  guaiacum  tincture,  and  then  a  drop  of  the  ether  reagent  added, 
when,  even  if  only  a  trace  of  the  coloring  matter  of  blood  be  present, 
a  blue  color  will  immediately  or  very  quickly  appear.     A  drop  of  a 


710  BLOOD. 

1-lOOOth  solution  of  blood  will  thus  immediately  yield  a  decided 
blue  coloration ;  and  a  l-5000th  solution  a  quite  distinct  reaction. 

The  test  may  be  applied  directly  to  the  stain,  if  on  a  white 
fabric,  by  moistening  it  with  a  drop  of  water,  and  then  adding  the 
guaiacum  and  ethereal  solutions.  Even  the  minutest  shred  of  a 
blood-stained  fabric  may  show  this  coloration.  When  the  stain  is 
on  colored  material,  it  may  be,  as  advised  by  Dr.  Taylor,  thoroughly 
soaked  with  a  drop  of  water,  and  the  liquid  absorbed  by  slips  of 
white  bibulous  paper;  these,  while  still  moist  or  after  they  have 
dried,  are  submitted  to  the  action  of  the  reagents. 

This  test  will  react  even  with  very  old  stains,  provided  they  are 
first  well  moistened  with  water ;  and  even  when  the  stains  have  been 
washed,  evidence  of  their  nature  may  be  obtained. 

In  one  of  our  experiments,  a  piece  of  muslin  1-lOth  of  an  inch 
square,  containing  a  moderate  blood-stain  of  ten  years'  standing,  was 
macerated  with  a  few  drops  of  water  for  ten  hours ;  the  liquid, 
which  had  acquired  only  a  faint  reddish  hue,  was  then  decanted  and 
evaporated  spontaneously,  when  it  left  a  smooth,  ring-like  deposit 
of  a  faintly  reddish-yellow  color.  This,  under  the  action  of  the  test, 
immediately  assumed  a  deep  blue  color.  So,  also,  a  minute  portion 
of  a  single  thread  of  the  soaked  material  immediately  acquired  a 
deep  blue  color  on  the  application  of  the  reagents. 

For  the  extraction  of  the  coloring  matter  of  very  old  blood- 
stains, M.  Blondlot  strongly  advises  [Annates  d'Hygihne,  1868,  i. 
130)  the  use  of  ammoniated  alcohol  (1 :  20).  This  we  have  found  a 
very  good  mixture  for  the  purpose.  A  little  potassium  hydrate  (free 
from  nitrite)  may  also  be  used  for  the  extraction,  the  liquid  being 
neutralized  with  acetic  acid  before  adding  the  guaiacum  tincture. 
D.  Vitali  has  observed  that  guaiacum,  when  precipitated  from  its 
alcoholic  solution  by  water  in  the  presence  of  haemoglobin,  carries 
down  with  it  the  whole  of  the  latter,  even,  he  states,  when  forming 
only  l-100,000,000th  of  the  liquid.  The  precipitate  is  then  col- 
lected and  tested  by  the  ether  solution.  (Jour.  Chem.  Soc.  Abst, 
1880,  926.)  On  collecting  the  precipitate,  however,  according  to 
our  experience,  it  sometimes  acquires  a  faint  blue  color  even  in  the 
absence  of  blood  and  before  the  ether  reagent  is  added,  due  to  slow 
oxidation. 

For  the  recovery  of  the  blood  coloring  matter  when  under  great 
dilution  in  water,  the  urine,  and  other  liquids,  it  may  be  precipi- 


CHEMICAIi   PR0PERTIE8.  711 

tated,  as  advised  by  Sclnvarz,  hy  zinc  acetate.  The  solution  is 
treated  witii  a  little  of  the  salt,  and  tlu;  mixture  allowed  to  stand 
several  hours,  or  until  the  precipitate  has  eoinj)lctely  subsided ;  the 
latter  is  then  collected  on  a  filter,  washed,  and  tested  by  the  guai- 
acuni  and  ether  reagents.  In  this  manner  we  have  obtained  very 
satisfactory  evidence  of  the  presence  of  blood  when  forming  only 
1 -50,000th  of  the  solution. 

Fallacies. — As  the  bluing  of  the  guaiacum  resin  in  this  test  is 
simply  due  to  oxidation,  a  like  result  is  produced  by  various  other 
substances,  organic  and  mineral,  especially  certain  salts  of  iron,  even 
in  very  minute  quantity.  But  all  these  substances,  according  to  Dr. 
Taylor,  who  has  critically  examined  this  test  (Guy's  Hosp.  RepoHs, 
1868,  431),  effect  the  bluing  loiihout  the  aid  of  the  hydrogen  solution  ; 
whereas  blood  does  not;  moreover,  they  have  not  the  color  of  blood. 
According  to  this  author,  there  is  no  red  coloring  matter  known,  other 
than  that  of  blood,  that  will  yield  these  results  under  the  action  of 
the  test.  If  the  reagent  solutions  be  applied  in  a  state  of  mixture, 
as  is  sometimes  advised,  the  results  are  open  to  serious  objections.  In 
the  examination  of  a  suspected  stain,  the  result  of  the  guaiacum 
solution  alone  should  first  be  determined;  and  after  the  addition  of 
the  ether  reagent  the  blue  coloration  should  appear  very  promptly, 
otherwise  the  result  would  be  very  doubtful. 

4.  Hcemin  Crystals. — When  heated  with  acetic  acid  and  a  little 
common  salt,  the  haemoglobin  of  the  blood  undergoes  decomposition, 
with  the  formation,  as  one  of  its  products,  of  hcematin,  which,  uniting 
with  hydrochloric  acid  produced  from  the  sodium  chloride,  forms 
hccmatin  hydrochloride,  or  hcemin.  This  compound  readily  crystallizes, 
forming  what  are  known  as  Teichraann' s  crystals,  he  having  first 
described  them,  in  1853;  its  composition,  according  to  Hoppe-Seyler, 
is  C^3H7()N8Fe20io,2HCl.  For  its  preparation,  the  blood  should  be 
in  the  dried  state,  and  only  the  most  concentrated  glacial  acetic  acid 
employed. 

When  the  blood  is  in  solution,  a  drop  of  the  liquid  is  evaporated 
to  dryness  on  a  thin  glass  slide  or  in  a  watch-glass,  the  residue  scraped 
together  and  pulverized,  a  trace  of  finely-powdered  salt  added,  and 
then  a  drop  or  two  of  the  acid.  The  heat  of  a  very  small  flame  of 
a  spirit-lamp  is  now  applied  to  the  mixture,  first  around  and  slightly 
beyond  the  edges  of  the  dispersed  liquid,  until  it  has  collected  on  the 
centre  of  the  slide  in  the  form  of  a  globule.     This  is  then  heated 


712  BLOOD. 

until  bubbles  of  gas  appear  and  the  liquid  acquires  a  reddish-brown 
color,  when  the  heat  is  gradually  withdrawn  until  only  a  minute  por- 
tion of  liquid  remains,  this  being  allowed  to  evaporate  by  the  heat 
of  the  slide. 

The  residue  thus  obtained  usually  consists  of  brownish-red  lines 
or  stains,  more  or  less  curved  or  circular  in  form.  Under  the  micro- 
scope the  hsemin  will  appear  as  minute  crystals,  of  a  yellowish, 
reddish,  or  brown  color,  more  or  less  transparent,  and  frequently 
arranged  in  the  form  of  stellate  groups,  Plate  XV.,  fig.  5.  When 
from  only  a  minute  quantity  of  blood,  the  crystals  are  single,  and 
usually  range  in  size  from  1-1 200th  to  1-1 800th  of  an  inch  in  length, 
and  from  l-6000th  to  1-1 2000th  of  an  inch  in  width. 

Under  this  test,  1-1 00th  of  a  grain  of  blood  will  yield  a  residue 
in  which  the  crystals  may  readily  be  recognized  under  a  power  of 
75  diameters.  From  l-500th  of  a  grain  the  crystals  are  usually 
so  minute  as  to  require  a  high  power  for  their  identification,  Plate 
XV.,  fig.  6.  With  care,  crystals  may  be  obtained  from  even  the 
1-lOOOth  of  a  grain  of  blood. 

Sometimes  the  hsemin,  even  under  a  high  power,  is  in  the  form 
of  opaque,  irregular  granules.  When  this  is  the  case,  the  residue  is 
again  treated  with  a  trace  of  salt  and  heated  with  acetic  acid.  Unless 
the  blood-stain  be  very  old  or  had  been  washed,  the  addition  of  the 
salt  is  not  essential,  as  the  quantity  normally  present  in  blood  is 
sufficient  for  the  purpose.  It  is  always  best,  however,  to  add  a 
minute  quantity  of  salt,  as  its  crystals  interfere  but  little  with  the 
recognition  of  those  of  hsemin,  and  they  may  readily  be  removed  by 
a  drop  of  water. 

Hsemin  crystals  are  insoluble  in  water,  alcohol,  and  acetic  and 
hydrochloric  acids,  sparingly  soluble  in  ammonia,  but  freely  so  in 
the  fixed  alkalies.  Under  the  action  of  the  guaiacum  test,  they  im- 
mediately assume  a  deep  blue  color.  The  crystals  may  be  mounted 
in  Canada  balsam  and  thus  preserved  indefinitely. 

When  the  stains  are  very  old  or  have  been  washed,  and  also 
when  they  are  recent,  a  small  portion  of  the  stained  fabric  or  of  the 
dried  clot  may  be  heated  in  a  very  small  test-tube  with  a  few  drops 
of  the  acetic  acid  and  a  little  salt  to  about  the  boiling  temperature, 
until  the  liquid  acquires  a  reddish  or  brown  color.  The  liquid  is 
then  transferred  by  a  capillary  pipette  to  a  watch-glass  and  evaporated 
as  above  directed.      In  this  manner  a  very  satisfactory  crystalline 


CIIEMICAI.    PROPERTIES.  713 

residue  was  obtained  from  1-lOtli  of  an  inch  squan;  ol"  a  fabric  con- 
taining a  blood-stain  ten  years  old. 

So  lonii;  as  any  of  the  coloring:;  matter  or  hfoinatin  remains  unde- 
composed,  crystals  may  be  obtained  by  this  test.  But  it  must  be 
borne  in  mind,  as  pointed  out  by  Struve,  that  a  blood-stain  may  have 
undergone  such  change  as  no  longer  to  respond  to  this  test,  its  color 
being  due  to  the  products  of  decomposition.  Hence  a  failure  to 
obtain  crystals  should  not  be  regarded  as  proof  of  the  absence  of 
blood.  Moreover,  it  is  sometimes  quite  difficult  to  obtain  crystals 
from  minute  quantities  of  blood,  even  when  recent.  And,  again, 
the  presence  of  certain  substances,  especially  free  acids,  except  acetic 
acid,  may  interfere  with  their  formation. 

Various  methods  have  been  advised  for  the  precipitation  of  the 
coloring  matter  of  the  blood  when  under  great  dilution  for  the 
application  of  this  test.  That  by  acetate  of  zinc  has  already  been 
mentioned  when  considering  the  guaiacum  test.  Another  is  to  treat 
the  solution  with  a  little  ammonia,  then  tannic  acid,  and  finally 
excess  of  acetic  acid,  and  allow  the  mixture  to  stand  twelve  or 
twenty-four  hours.  The  dark  brownish  precipitate  is  collected, 
washed,  and  subjected  to  the  action  of  the  test,  a  portion  being  exam- 
ined by  the  guaiacum  method.  Satisfactory  results  may  be  obtained 
by  this,  as  also  by  the  zinc  method,  from  solutions  containing  only 
l-50,000th  of  blood. 

Fallacies. — The  forms  and  appearances  of  hsemin  crystals  are  so 
peculiar  and  striking  that  they  could  not  be  confounded,  at  least  by 
any  one  familiar  with  their  characters,  with  any  other  substance. 
Their  production  is  characteristic  of  blood,  there  being  no  other 
substance  known  from  which  they  can  be  obtained. 

It  has  been  asserted  that  the  crystals  from  the  blood  of  different 
animals  differ  somewhat  in  appearance ;  but  this  is  an  error,  since 
they  are  essentially  the  same  in  form  and  character  as  produced  from 
the  blood  of  all  vertebrate  animals. 

Of  the  various  other  chemical  methods  that  have  been  proposed 
for  the  detection  of  blood  there  need  only  be  mentioned  that  of  M. 
Sonnenschein  (1873).  This  consists  in  treating  a  solution  of  the  stain 
with  a  solution  of  sodium  molybdate  or  tungstate  strongly  acidulated 
with  acetic  or  phosphoric  acid,  whereby  a  precipitate  is  produced  which 
under  a  gentle  heat  collects  into  a  pulverulent,  brownish  mass.    This, 


714 


BLOOD. 


when  collected  and  gently  heated  with  a  few  drops  of  aqua  ammonise, 
dissolves  to  a  solution  which  appears  of  a  dark  red  color  by  reflected, 
and  greenish  by  transmitted,  light.  This  dichroism  will  still  appear 
when  obtained  from  a  blood  solution  so  dilute  as  to  have  only  a  faint 
red  color.  The  precipitate  is  reproduced  on  addition  of  excess  of 
acetic  acid,  and  may  then  be  examined  by  the  guaiacum  test. 

III. — Optical  Properties  of  Blood. 

History. — When  light  that  has  passed  through  a  solution  of  blood 
is  received  upon  a  prism,  the  spectrum  produced  presents  character- 
istic black  bands,  the  corresponding  portions  of  the  light  having 
been  absorbed  by  the  coloring  matter  of  the  blood.  This  fact  was 
first  observed  by  Hoppe-Seyler,  in  1862,  and  he  proposed  it  as  a 
means  of  detecting  the  presence  of  blood  in  medico-legal  investiga- 
tions. 

A  few  years  later,  1864,  Prof.  Stokes  found  that  two  distinct 
spectra  might  be  obtained  from  the  blood,  depending  upon  the  state 
of  oxidation  of  its  coloring  matter,  the  one  corresponding  to  arterial 
blood  and  the  other  to  deoxidized  or  venous  blood.     Further  re- 
searches have  shown  that  under 
the  action  of  chemical  reagents  a 
number  of  characteristic  spectra 
may  thus  be  obtained  from  hae- 
moglobin, and  its  products  and 
compounds. 

Application. — For  the  appli- 
cation of  this  method  in  con- 
nection with  the  microscope,  the 
instrument  known  as  the  Sorby- 
Browning  spectroscope  eye-piece, 
or  micro-spectroscope,  is  admira- 
bly adapted.  Fig.  14.  This  in- 
strument permits  two  spectra  to 
be  examined  at  the  same  time, 
and  thus  the  spectrum  of  the 
suspected  substance  may  be  com- 
pared side  by  side  with  that  of  a 
known  sample  of  blood.  Any  microscope,  provided  the  eye-piece 
fits,  will  answer  this  purpose;  but  it  is  somewhat  more  convenient 


Sorby's  spectroscope  eye-piece. 


OPTICAL    PROPERTIES.  715 

to  employ  :i  hinociilar  instrument.  Only  low  |)ovvcrs,  such  as  the 
one  and  a  half  or  two-thirds  inch,  are  required  for  the  examination. 
It  is  well  to  cut  ofl'all  extraneous  light  from  the  front  of  the  objective 
by  placing  over  it  a  capped  tube  having  a  small  perforation  in  the 
centre  of  the  cap. 

The  solution  to  be  examined  may  be  placed,  as  advised  by  Mr. 
Sorby,  in  small  cells  about  half  an  inch  deep,  made  from  barometer 
tubing,  and  cemented  to  a  glass  plate.  These  cells  permit  the  ex- 
amination of  a  long  column  with  only  a  small  amount  of  fluid,  and 
are  convenient  for  the  addition  of  reagents.  But  the  examination 
may  be  made  with  a  small  drop  of  the  solution  placed  simply  on 
a  glass  slide.  Either  ordinary  or  artificial  light  may  be  employed  : 
the  latter  is  usually  to  be  preferred. 

The  focus  of  the  microscope  having  been  adjusted  to  the  sur- 
face of  the  blood  solution,  and  the  slit  of  the  spectroscope  so  nar- 
rowed as  to  allow  only  sufficient  light  to  pass,  the  appearances  pre- 
sented will  depend  somewhat  on  the  age  of  the  blood,  the  strength 
of  the  solution,  and  also,  in  part,  the  length  of  the  column  of  fluid 
examined. 

1.  Oxy-JHcemoglobin. — When  the  blood  is  fresh  and  the  solution 
not  too  strong,  more  or  less  of  the  blue  end  of  the  spectrum  is  ab- 
sorbed, and  two  characteristic  bands  appear  in  the  green  portion  of 
the  spectrum.  Of  these  bands,  the  one  towards  the  red  end  of  the 
spectrum  nearly  or  altogether  touches  Fraunhofer's  line  D,  is  darker 
in  appearance,  sharper  in  outline,  and  narrower  than  the  other,  wdiich 
is  placed  near  the  line  E,  Chromo-lithograph,  Spectrum  2.  In 
stronger  solutions  these  bands  unite,  and  may  occupy  the  entire  space 
between  D  and  E. 

In  a  deep  cell,  such  as  above  described,  a  solution  containing 
1-oOOth  of  its  weight  of  blood  gives  the  spectrum  in  great  perfection  ; 
in  a  1-lOOOth  solution  the  bands  are  still  well  marked,  though  some- 
what narrowed.  Under  much  dilution,  the  band  next  Fraunhofer's 
line  E  diminishes  in  intensity  more  rapidly  than  its  fellow.  The 
delicacy  of  this  test  is  such,  in  fact,  that  with  proper  manipulation, 
as  first  announced  by  Mr.  Sorby,  a  faint  spectrum  may  be  obtained 
from  even  a  single  blood-corpuscle. 

These  results  are  wholly  due  to  the  oxy- haemoglobin  of  the 
blood,  of  which  it  forms  only  about  one-eighth  by  weight.  The 
differences  observed  in  the  spectra  of  solutions  of  oxy-hsemoglobin 


716  BLOOD. 

of  varying  degrees  of  dilution  have  been  described  and  figured  by 
W.  Preyer.     [Die  Blutkrystalle,  Jena,  1871.) 

2.  Hcemoglobin. — If  a  solution  of  fresh  blood  be  treated  with  a 
little  ammonia,  the  two  bands  become  somewhat  narrowed  and  sharper 
in  outline.  On  now  adding  a  little  citric  or  tartaric  acid,  avoiding 
excess,  and  then  stirring  in  the  solution  a  minute  crystal  of  ferrous 
sulphate,  preventing  free  access  of  air,  the  liquid  acquires  a  purple 
color,  and  exhibits  under  the  spectroscope  a  single  broad  band, 
extending  over  and  beyond  what  was  the  space  between  the  two 
former  bands.  Spectrum  3. 

This  is  the  spectrum  of  Iwemoglohin,  known  also  as  reduced  hcemo- 
globin, and  may  be  seen  in  blood-stains  or  solutions  that  have  be- 
come more  or  less  brown.  This  reduction  may  also  be  effected  by 
ammonium  sulphide,  without  the  other  reagents.  On  agitating  the 
reduced  mixture  with  air,  the  two  bands  of  oxy-hsemoglobin  reappear. 

If  in  this  experiment  the  citric  or  tartaric  acid  be  added  first, 
and  then  the  ammonia  and  iron  salt,  the  mixture  assumes  a  brown 
color  and  presents  the  spectrum  of  reduced  hcematin. 

3.  Methcemoglobin. — In  blood  that  has  been  exposed  to  the  nir 
for  some  time  and  become  more  or  less  brown,  there  is  gradually 
formed  a  substance  named  by  Hoppe-Seyler  methcemoglobin.  Tlie 
exact  nature  of  this  substance  is  not  yet  fully  understood.  Accord- 
ing to  Hoppe-Seyler,  it  is  an  oxide  of  haemoglobin  containing  less 
oxygen,  and  this  more  firmly  combined,  than  is  present  in  oxy- 
hsemoglobin.  {Physiol.  Chem.,  1881,  391.)  This  compound  may  be 
produced  at  once  by  treating  a  solution  of  blood  with  potassium 
permanganate  solution. 

The  spectrum  of  methcemoglobin  presents  a  deep  band  in  the  red, 
and  usually  two  bands  more  or  less  faint  in  the  green,  Spectrum  4. 
In  the  conversion  into  this  substance,  the  band  in  the  red,  at  first 
only  very  feeble,  gradually  increases  in  intensity,  whilst  the  bands  in 
the  green  gradually  become  more  feeble  and  are  finally  lost.  Mr. 
Sorby  found  that  while  it  usually  required  some  weeks  to  effect  this 
change  in  a  pure  country  atmosphere,  it  might  take  place  within  a 
few  hours  in  the  impure  air  of  a  city.  We  have  seen  the  change 
only  moderately  marked  in  a  stain  three  weeks  old. 

If  a  little  ammonium  sulphide  be  added  to  the  methsemoglobin 
solution,  the  band  in  the  red  disappears  and  the  broad  band  of 
haemoglobin  appears  in  the  green.     This  may  now  be  oxidized,  by 


OPTICAL   PROPERTIES.  717 

exposure  to  the  air,  to  oxy-hffimo^lobin.  jMcthaemoglobin  has 
recently  been  obtained  in  the  crystalline  state  by  Hiifncr  and  Otto. 
(Zeiis.  f.  Phys.  C/iem.,  vii.  1883,  G5.) 

4.  Hcemat'm. — When  blood  is  exposed  to  the  action  of  the  air 
for  long  periods,  the  haemoglobin  undergoes  complete  decomposi- 
tion, giving  rise,  with  other  products,  to  hccmatln,  which  is  more 
stable  in  its  nature  than  haemoglobin,  and  may  resist  decomposition 
for  many  years.  A  stain  in  which  this  change  has  taken  place  is  no 
longer  soluble  in  water,  but  may  be  dissolved  by  diluted  acids. 

Tliis  conversion  is  effected  immediately  on  treatino;  fresh  blood 
with  an  acid.  Hence,  if  a  solution  of  blood,  either  fresh  or  old,  be 
treated  with  a  little  acetic  or  citric  acid,  the  spectrum  of  add  hcema- 
tin  will  appear,  in  which  there  is  an  absorption  band  in  the  red  and 
another  in  the  green.  Spectrum  5.  Sometimes,  according  to  the 
strength  of  the  solution,  the  band  in  the  green  is  absent,  whilst  at 
other  times  two  faint  bands  may  be  seen  in  the  green.  It  need 
hardly  be  stated  that  when  lisemalin  has  once  been  formed,  it  is  no 
longer  possible  to  obtain  the  spectra  of  haemoglobin  and  its  oxides. 

5.  Alkaline  Hcematin. — If  to  the  solution  of  acid  haematin  slight 
excess  of  ammonia  be  added,  the  spectrum  of  alkaline  hcematin,  having 
a  single  broad  band  in  the  red,  will  manifest  itself.  Spectrum  6. 
With  stronger  solutions,  according  to  Preyer,  the  band  extends 
beyond  the  line  D. 

6.  Reduced  Hcematin. — On  adding  a  little  ferrous  sulphate  to  the 
last-mentioned  solution,  it  will  exhibit  the  spectrum  of  reduced 
hcematin,  Spectrum  7,  as  figured  by  Preyer.  This  spectrum  closely 
resembles  that  of  a  somewhat  dilute  solution  of  oxy-haemoglobin, 
only  that  the  two  bands  are  slightly  moved  towards  the  blue  end 
of  the  spectrum.  This  substance  has  been  named  by  Hoppe-Seyler 
hcemochromogen. 

The  three  haematin  spectra  usually  exhibit  themselves  more 
strongly  marked  than  the  spectrum  of  haemoglobin  under  like  con- 
ditions. These  spectra  may  be  obtained  from  blood-stains  after  the 
lapse  of  many  years. 

7.  Carbonic  oxide  Hcemoglohin. — In  fatal  asphyxia  from  car- 
bonic oxide  gas,  as  is  well  known,  the  blood  acquires  a  peculiar 
rose-red  color,  which  it  may  retain  for  long  periods.  In  poisoning 
by  this  substance,  the  carbonic  oxide  unites  with  the  haemoglobin  of 
the  blood  to  form  carbonic  oxide  hcemoglohin,  the  gas  taking  the  place. 


718  BLOOD. 

volume  for  volume,  of  oxygen  in  the  formation,  by  the  latter,  of 
oxy-hsemoglobin.  This  compound  is  not  decomposed  by  the  oxygen 
of  the  air,  and  it  more  strongly  resists  the  action  of  reducing  agents 
and  putrefaction  than  do  the  oxides  of  hsemoglobin. 

Accepting  Prof.  Hiifner's  formula  for  hsemoglobin,  the  molecular 
composition  of  the  carbonic  oxide  compound,  according  to  the  re- 
searches of  my  assistant,  Dr.  J.  Marshall,  while  in  Prof.  Hiifner's 
laboratory,  is  CgjgHioss^ieiFeSsOigg-CO,  its  molecular  weight  being 
14,157.     {Zeits.  fur  Phys.   Chem.,  Jan.  1883,  81.) 

The  spectrum  of  carbonic  oxide  hsemoglobin,  shown  in  Spectrum 
8  (after  Preyer),  is  very  similar  to  that  of  oxyhsemoglobin,  only  that 
the  two  bands  are  of  equal  intensity  and  about  equal  in  width.  Its 
strong  resistance  to  reducing  agents  readily  distinguishes  it  from  the 
spectrum  of  oxy-hsemoglobin.  Thus,  when  the  solution  is  treated 
with  a  drop  or  two  of  ammonium  sulphide,  the  two  bands  remain 
unchanged;  whereas  with  oxyhsemoglobin  they  are  immediately  re- 
placed by  the  single  band  of  hsemoglobin.  Indeed,  Prof.  Vogel  has 
proposed  this  property  as  a  test  for  the  presence  of  carbonic  oxide  in 
the  atmosphere,  by  exposing  to  the  air  a  single  drop  of  fresh  blood, 
and  then  adding  to  the  liquid  the  ammonium  salt,  when,  if  the  air 
contains  only  0.3  per  cent,  of  the  gas,  the  reduction  will  be  prevented. 
{Chem.  News,  1877,  i.  184.) 

Examination  of  Suspected  Stains. — In  the  practical  appli- 
cation of  the  spectroscopic  method  to  a  suspected  stain,  the  proce- 
dure will  depend  somewhat  upon  the  amount  of  material  at  com- 
mand and  the  age  of  the  stain.  When  the  stain  is  fresh,  it  requires 
only  a  small  amount  of  blood  to  furnish  the  various  spectra  above 
described. 

When  on  a  fabric  and  at  least  of  moderate  size,  a  portion  of  the 
stained  material  is  macerated  with  a  little  water  in  a  small  tube  or 
watch-glass,  and  any  red  solution  obtained,  after  subsidence  of  sus- 
pended matters,  transferred  to  a  deep  cell  and  examined.  If  the 
liquid  exhibits  the  spectrum  of  oxy-hsemoglobin,  a  little  ammonia 
may  be  added,  then  a  minute  crystal  of  citric  acid,  avoiding  excess, 
and  finally  a  little  ferrous  sulphate,  when,  as  the  latter  dissolves, 
the  spectrum  of  hsemoglobin  will  appear. 

Or,  the  solution  which  showed  the  two  bands  of  oxy-hsemoglobin 
may  be  treated  with  a  little  citric  acid,  when  the  bands  will  disap- 
pear, and  the  bands  of  acid   hsematin   may  or  may  not  appear ;  on 


EXAMINATION    OF  SUSPECTED   STAINS.  719 

the  subsequent  addition  of  ammonia  and  then  fVrrous  sulphate,  the 
spectrum  of  reduced  hsematin  will  be  developed.  From  dilute  solu- 
tions this  spectrum  is  more  readily  obtained  than  that  of  reduced 
hcBnioj^lobin.  A  blood-stain  only  1-lOth  of  an  inch  square,  if  readily 
soluble,  will  suffice  to  show  these  spectra  in  a  very  marked  degree. 
If  the  solution  has  only  a  faint  red  hue,  a  very  narrow  and  deep  cell 
should  be  employed.  When  the  stain  is  on  colored  material,  an 
equal  portion  of  the  unstained  fabric  should  be  examined  in  a  simi- 
lar manner.  If  the  stain  is  sufficiently  thick  to  permit  the  separation 
of  solid  particles,  these  should  be  dissolved  in  a  drop  or  two  of 
water  and  examined. 

Should  the  solution  first  obtained  exhibit  the  spectrum  of  met- 
haemoglobin,  it  may  be  further  examined  in  the  manner  already 
indicated.  A  blood-stain  in  which  this  change  has  taken  place  may 
be  only  partially  soluble  in  water,  a  portion  of  the  coloring  matter 
having  been  further  changed  into  hsematin,  which  is  insoluble  in 
water. 

If  the  stain  is  old  or  has  been  washed,  it  may  be  wholly  insoluble 
in  pure  water.  Under  these  circumstances  it  is  treated  with  a  few 
drops  of  water  containing  a  little  citric  or  acetic  acid,  and  digested 
at  the  ordinary  temperature  for  several  hours,  if  necessary.  Any 
brownish  or  yellowish  liquid  thus  obtained  is  examined  for  the 
spectra  of  haematin  in  its  acid,  alkaline,  and  reduced  states.  In 
very  dilute  solutions,  as  already  indicated,  the  spectrum  of  reduced 
haematin  may  sometimes  be  obtained  when  there  is  a  failure  to 
obtain  that  of  either  acid  or  alkaline  htematin.  From  a  stain  seven- 
teen years  old,  in  wdiich  the  coloring  matter  was  wholly  changed 
into  haematin,  Dr.  Letheby  {London  Hosp.  Rep.,  iii.  41)  obtained 
from  a  portion  of  the  fabric  not  exceeding  one-fourth  inch  in  diam- 
eter only  faint  traces  of  the  spectrum  of  acid  hiematin,  but  under 
the  action  of  ammonia  and  then  of  ferrous  sulphate  he  obtained  as 
well-marked  spectra  as  from  comparatively  recent  blood. 

If  the  blood-stain  has  been  heated  or  washed  with  hot  water, 
dilute  acids  will  generally  fail  to  act  upon  it,  but  it  may  be  dissolved 
in  water  containing  a  little  ammonia,  especially  if  the  mixture  be 
heated.  The  solution  is  then  treated  with  a  little  citric  acid  and 
ferrous  sulphate  and  examined  for  reduced  hsematin.  For  this 
reduction  it  is  somewhat  better  to  substitute  for  the  citric  acid  the 
double  tartrate  of  potassium  and  sodium,  and  for  the  iron  salt  the 


720  BLOOD. 

double  ferrous  and  ammonium  sulphate ;  or,  the  ammoniacal  solution 
may  be  treated  at  once  with  ferrous  tartrate. 

When  the  stain  is  only  in  very  minute  quantity,  it  should  be 
carefully  examined  for  any  dried  clot,  which,  if  found,  is  placed  on 
a  glass  slide,  moistened  with  a  very  minute  drop  of  diluted  glycerine 
(1  : 5),  and  any  solution  obtained  examined  directly  by  the  spectro- 
scope. In  this  manner  we  have  found,  as  stated  by  Dr.  J.  G. 
Richardson  [Med.  Times,  Nov.  1875,  78),  that  a  clot  not  exceeding 
1-1 00th  of  an  inch  in  diameter  will  yield  a  very  satisfactory  spectrum. 
Dr.  Richardson  advises  to  place  the  minute  clot  moistened  with 
the  glycerine  on  a  thin  glass  cover,  and  then  invert  this  over  the 
concaved  centre  of  a  slide :  it  may  then,  after  examination  by  the 
spectroscope,  be  examined  under  a  higher  power  for  the  presence  of 
blood-corpuscles,  and  finally  by  the  guaiacum  test.  If  no  clot  is 
found,  a  shred  of  the  stained  fabric  may  be  moistened  with  diluted 
glycerine  and  examined  in  a  similar  manner.  The  solvent  action 
of  moderately  diluted  glycerine  upon  somewhat  old  blood-stains  is 
markedly  less  than  that  of  pure  water. 

Fallacies. — There  are  certain  other  coloring  substances  that  ex- 
hibit spectra  more  or  less  similar  in  appearances  to  those  of  blood. 
In  his  extended  examination  of  various  coloring  principles,  Mr. 
Sorby  found  the  spectrum  of  alkanet  root  in  alum  to  bear  the  closest 
resemblance  in  this  respect,  it  having  two  bands  in  the  green ;  but 
the  band  towards  the  red  is  the  broader  of  the  two,  whereas  the 
I'e verse  is  the  case  in  the  blood  spectrum. 

So,  also,  cochineal  presents  two  bands  in  the  green,  but  these  are 
about  equal  in  intensity  and  width.  Moreover,  neither  of  these 
substances  resists  the  action  of  ammonia,  nor  will  they  yield  the 
other  spectra  of  blood.  It  has  also  been  asserted  that  the  coloring 
matter  of  the  feathers  of  the  banana-eater  {Turacus  albocristatus)  of 
the  East  Indies  exhibits  a  spectrum  very  similar,  both  in  position 
and  appearance  of  the  bands,  to  that  of  fresh  blood ;  but  it  is  said 
to  be  unaffected  by  sodium  sulphide,  which  quickly  changes  the 
character  of  the  blood  spectrum. 

Prof.  Reichardt  has  asserted  (Arch.  d.  Pharm.,  1875)  that  the 
spectrum  of  purpurin  sulphuric  acid  might  be  confounded  with  that 
of  alkaline  hsematin.  According  to  Dr.  Ch.  Gauge,  of  Jena,  how- 
ever, this  substance  yields  its  spectrum  only  from  warm  solutions, 
and  the  band  lies  between  D  and  E,  whilst  that  from  blood  is 


MICROSCOPIC  DETECTION   AND   DISCRIMINATION.  721 

between  D  luul  C;  moreover,  although  the  spectrum  of  potassium 
purpurin  sulj)hatc  hears  great  siinihirity  to  tliat  of  hieinoglohin,  yet 
it  roinaiiis  unchanged  on  exposure  to  the  air,  whereas  hicmoglobin  is 
oxidized  to  oxy-lia)moglobin. 

Hence  these  fallacious  substances  differ  from  blood  in  most  in- 
stances in  the  position  and  character  of  the  spectral  bands,  and  in  aU 
cases  in  the  effect  of  reagents  upon  their  solutions.  At  present  there 
is  no  substance  known  that  in  all  these  respects  is  similar  to  the 
coloring  matter  of  blood. 

The  methods  thus  far  considered  simply  serve  to  answer  the 
question  whether  or  not  a  suspected  stain  or  substance  is  blood,  the 
results,  when  positive,  being  common  to  the  blood  of  man  and  all 
animals  having  red  blood.  Any  further  determination  as  to  whether 
it  is,  or  may  be,  the  blood  of  man,  or  the  kind  of  animal  from  which 
it  was  derived,  can,  so  far  as  at  present  known,  be  made  only  by 
means  of  the  microscope  in  determining  the  character  of  the  blood- 
corpuscles.  It  is  true  that  many  years  since  (1829)  M.  Barruel  pro- 
posed to  treat  the  blood  with  concentrated  sulphuric  acid,  when,  as 
he  claimed,  a  peculiar  odor  would  be  evolved  resembling  that  of  the 
cutaneous  exhalation  of  man  or  the  animal  from  which  the  blood  was 
derived.  But  numerous  observers  have  long  since  shown  that  no 
reliance  whatever  could  be  placed  in  this  method,  even  when  ap- 
plied to  fresh  blood  and  in  comparatively  large  quantity.  So,  more 
recently,  Adolph  Neumann  proposed  to  evaporate  the  blood  solution 
to  dryness  at  about  15.5°  C.  (60°  F.),  when  the  residue  would,  under 
the  microscope,  present  appearances  or  "  pictures,"  whereby  the  blood 
of  man  could  be  distinguished  from  that  of  animals  and  these  from 
one  another.  Numerous  colored  illustrations  of  the  appearances  thus 
presented  by  different  bloods  are  given  by  this  observer.  [Die  Er- 
kennung  des  Blutes  bei  gerichtlichen  Untersuchungen,  Leipsic,  1869.) 
On  examining  this  method,  however,  we  find  no  constancy  in  the 
appearances  of  the  same  blood,  and  even  different  portions  of  the 
same  residue  may  exhibit  widely  different  appearances. 

IV.  Microscopic  Determination  and  Discrimination  of  Blood. 

Oviparous  Blood. — Injudicial  investigations,  as  already  stated, 
it  is  sometimes  very  important  to  determine,  at  least,  whether  the 

46 


722  BLOOD. 

blood  is  that  of  an  oviparous  animal  or  that  of  a  mammal.  We 
have  already  seen  that  the  blood- corpuscles  of  all  oviparous  animals, 
including  birds,  rejDtiles,  and  fishes,  are  oval  in  form,  except  in  a 
small  family  of  the  last-named  class,  in  which  they  are  circular ; 
whereas  in  the  blood  of  all  mammals,  except  the  camel  tribe,  they 
are  circular  in  outline.  Moreover,  in  the  former  group  of  animals, 
without  exception,  the  corpuscles  have  each  a  nucleus,  whilst  in  the 
latter  and  in  man  they  are  destitute  of  a  nucleus.  Hence  this 
question  is  one  of  ready  solution  in  fresh  blood ;  but  when  the  blood 
is  in  the  form  of  dried  stains  the  distinction  may  be  difficult,  or  even 
impossible,  especially  if  the  stains  are  old. 

When  in  the  dried  state,  a  small  clot,  or  a  thread  of  the  stained 
fabric,  is  treated  on  a  glass  slide  with  a  drop  of  diluted  glycerine 
(1: 10),  then  covered  with  a  thin  glass,  and  examined  under  a  power 
of  about  400  diameters.  Sooner  or  later,  according  to  the  age  of  the 
blood,  unless  very  old,  the  mass  will  disintegrate  and  the  corpuscles 
may  be  seen  of  their  distinctive  characters.  For  this  purpose  it  is 
generally  more  satisfactory  to  employ  a  clot,  even  if  only  very  minute, 
than  a  stained  fibre. 

If  the  clot  is  so  old  and  dry  as  not  to  disintegrate  under  the 
action  of  the  diluted  glycerine,  the  moistened  mass  is  gently  crushed 
and  then  examined.  It  is  sometimes  better,  in  order  to  prevent  the 
distribution  of  the  liquid,  to  place  the  crushed  clot  on  the  thin  glass 
cover,  and  then,  after  addition  of  the  glycerine,  invert  this  over  a 
shallow  glass  cell  attached  to  a  glass  slide. 

On  examining  a  crushed  mass  of  this  kind  under  the  microscope, 
the  nuclei,  if  oviparous  blood,  and  the  outlines  of  the  corpuscles  of 
normal  form,  may  sometimes  be  distinctly  seen  in  the  thinner  por- 
tions and  margins  of  the  particles  before  any  disintegration  of  the 
mass  itself  has  taken  place.  We  have  thus  seen  the  nuclei  and 
outlines  most  distinctly  marked  in  thin  portions  of  oviparous  bloods 
that  had  been  loosely  preserved  in  paper  for  over  ten  years.  At 
times  only  the  nuclei  are  to  be  seen,  the  outlines  of  the  corpuscles 
themselves  being  wholly  invisible.  After  a  time  the  corpuscles 
become  more  or  less  detached  from  the  entangled  mass,  and  then 
their  nature  may  be  readily  determined. 

It  must  be  remembered  that  if  the  blood  be  treated  with  excess 
of  a  liquid  specifically  lighter  than  itself,  the  oval  corpuscles  may 
become  nearly  or  altogether  spherical  in  outline ;  but  under  these 


MICROSCOPIC   DETECrriON   AND   DISCRIMINATION.  723 

circumstances  the  nuclei  will  still  be  seen,  they  being  generally  much 
more  strongly  marked  than  the  outlines  of  the  corpuscles  themselves. 
When  the  outlines  are  not  well  marked  or  are  invisible,  they  may 
often  i)e  rendered  distinct  by  the  addition  of  a  little  iodine  solution. 
Carmine  and  aniline  may  also  be  employed  for  this  purpose.  Much 
may  often  l)e  done  in  rendering  the  outlines  visible  by  simply 
changing  the  light  from  the  mirror  of  the  microscope. 

The  following  method  for  this  differentiation,  advised  by  Dr.  R. 
M.  Bertolet  {Amer.  Jour.  Med.  *Se/.,  Jan.  1872,  128),  may  sometimes 
be  used  with  great  advantage.  The  dried  blood  is  treated  with  a 
small  drop  of  pure  glycerine  slightly  acidulated  with  acetic  acid, 
whereby  the  nuclei,  when  present,  are  rendered  more  distinct.  On 
now  adding  a  little  fresh  tincture  of  guaiacum,  and  then  a  drop  of 
"ozonic  ether,"  the  nuclei  will  appear  sharply  defined  and  of  a  dark 
blue  color,  while  the  surrounding  portions  of  the  corpuscles  will  have 
a  delicate  violet  hue  or  may  remain  uncolored.  With  recent  blood 
and  that  of  moderate  age  this  method  yields  well-marked  results; 
but  with  older  stains  the  guaiacum  reagents  produce  little  or  no  effect, 
since  the  coloring  matter  is  then  unacted  upon  by  pure  glycerine. 

Mammalian  Blood. — When  the  foregoing  examination  has 
shown,  or  it  is  admitted,  that  the  blood  is  that  of  a  mammal,  the 
question  may  then  arise.  In  how  far  can  the  blood  of  man  and  the 
blood  of  other  mammals  be  distinguished  from  each  other? 

Our  ability  to  answer  this  question  will  obviously  depend  upon, 
(1)  how  far  the  red  corpuscles  of  the  different  mammals  differ  from 
one  another  in  average  size ;  and  (2)  our  ability  to  appreciate  or 
measure  such  differences.  Reversing  the  order  of  these  propositions, 
we  may  consider, — 

1.  Limit  of  Determinln'o  Differences. 

a.  By  the  unaided  Eye. — With  an  ordinary  rule  divided  into 
1-lOOths  of  an  inch  the  unaided  eye  will  measure  the  distance 
between  two  points,  or  the  centres  of  two  fine  linas,  with  considerable 
accuracy  to  within  one-half  division,  and  in  some  cases  even  less, — 
that  is,  to  within  l-200th  of  an  inch,  or  less.  By  transmitted  light, 
fine  lines  ruled  on  glass,  with  their  centres  l-200th  of  an  inch  apart, 
are,  with  the  interspaces,  readily  distinguished  by  the  naked  eye. 

Very  minute  differences  in  the  size  of  objects  may  thus  be  detected. 


724  BLOOD. 

Thus,  if  two  discoidal  diatoms  (arachnoidiscus)  measuring  respec- 
tively l-139th  and  l-166th  of  an  inch  in  diameter  be  placed  side 
by  side  on  a  glass  slide,  they  are  readily  discriminated  in  size  by 
transmitted  light,  although  their  diameters  differ  by  only  l-854th 
of  an  inch.  It  is  true  that  the  difference  of  the  areas  in  this  instance 
aids  the  eye  in  the  distinction,  this  difference  being,  however,  only 
l-82,317th  of  a  square  inch. 

In  like  manner,  as  we  have  found  by  experiment,  many  persons 
can  readily  distinguish,  by  the  unaided  eye,  the  long  from  the  short 
diameter  of  a  single  oval  blood-corpuscle  of  the  Proteus,  measuring 
l-450th  by  l-850th  of  an  inch,  the  difference  of  the  diameters 
being  l-956th  of  an  inch. 

b.  By  the  Microscope. — Our  ability  thus  to  discriminate  minute 
differences  will  obviously  be  increased  in  proportion  as  the  size  of 
the  object  is  apparently  increased.  As  is  well  known,  it  is  not  the 
object  itself  that  is  seen  in  the  eye-piece  of  a  compound  microscope, 
but  the  image  of  the  object  placed  upon  the  stage. 

Thus,  under  an  amplification  of  ten  diameters,  the  1-1 000th  of 
an  inch  of  an  object  becomes  apparently  1-lOOth  of  an  inch ;  and 
under  a  power  of  one  hundred,  the  diameter  of  an  object  is  increased 
one-hundredfold,  the  l-10,000th  of  an  inch  now  being  represented 
by  1-lOOth  of  an  inch.  So,  in  like  manner,  under  one  thousand 
diameters,  the  1-lOOth  of  an  inch  of  the  image  corresponds  to  only 
l-100,000th  of  an  inch  of  the  object,  and  now  the  latter  can  be 
measured  to  within  the  1-1 00,000th  of  an  inch  with  the  same  degree 
of  accuracy  that  an  ordinary  object  can  be  measured  to  1— 100th  of 
an  inch  by  the  unaided  eye. 

The  effect  of  amplification  is  strikingly  shown  in  Fig.  15,  in 
which  the  inner  circle  or  disk  represents  the  ap- 
^^"  parent  size  of  an  object  1-lOOOth  of  an  inch 

in  diameter  under  a  power  of  10  diameters ;  the 
second,  the  same  under  a  power  of  100 ;  and  the 
outer,  the  original  when  amplified  1000  times. 

If  three  blood-corpuscles,  measuring  respec- 
tively l-3000th,  l-3500th,  and  l-4000th  of  an 
inch  in  diameter,  be  examined  under  a  power  of 
400  diameters,  they  will  appear,  in  round  num- 
bers, 13-lOOths,  11-lOOths,  and  10-lOOths  of  an  inch  in  diameter; 
under  1000  diameters,  38-lOOths,  28-lOOths,  and  25-lOOths  of  an 


MICROSCOPIC  DETECmON    AND   DISCRIMINATION.  725 

inch;  and  under  a  power  of  2/300,  they  will  measure  83-lOOtlis, 
71-lOOths,  and  62-lOOtlis  of  an  inch  respectively.  Under  the 
last-named  power,  there  would  be  an  (ij)j)(!rcn(  diflerence  of  1-lOOth 
of  an  inch  in  the  diameters  of  two  corpuscles  measuring  respectively 
l-3200th  and  l-3240th  of  an  inch  in  diameter. 

In  the  amplification  of  blood-corpuscles,  however,  there  is  a  limit 
beyond  which  any  increase  of  apparent  size  is  attended  with  more  or 
less  loss  of  sharpness  of  outline,  which  is  essential  for  exact  measure- 
ment. Exactly  where  this  limit  lies  will  depend  much  on  the  excel- 
lency of  the  optical  parts  of  the  instrument  employed. 

Measurement  by  the  Mici^oscope. 

Stage  Micrometer. — Among  the  appliances  necessary  for  micro- 
metric  measurement  is  a  stage  micrometer  of  known  value.  This 
usually  consists,  according  to  English  measurement,  of  a  series  of 
fine  lines  ruled  upon  glass  at  a  distance  from  each  other  of  1-lOOth 
of  an  inch,  one  of  the  divisions  being  subdivided  into  tenths,  or 
thousandths  of  an  inch.  Other  fractions  of  an  inch  are  sometimes 
added  to  the  scale. 

As  these  subdivisions  of  1-lOOOth  inch,  as  found  in  scales,  are 
by  no  means  always  exactly  equal,  the  scale  before  being  used  should 
be  carefully  examined  in  this  respect,  under  a  high  power.  If  it  is 
found  that  the  spaces  are  unequal  in  value,  it  should  then  be  de- 
termined whether,  at  least,  any  one  of  the  subdivisions  represents 
exactly  the  one-tenth  of  the  1-lOOth  inch  division,  and  this,  if 
found,  should  be  employed  as  the  standard.  We  have  seen  scales 
in  which  the  discrepancy  between  certain  spaces  amounted  to  l-35th 
of  a  subdivision  (l-35,000th  of  an  inch). 

Eye-piece  Micrometer. — Employing  the  stage  micrometer  as  the 
standard,  measurements  may  be  made  by  means  either  of  a  cobweb 
micrometer,  the  eye-piece  micrometer,  or  the  camera  lucida.  Of  these 
methods,  and  others  that  might  be  mentioned,  only  that  by  means 
of  Jackson's  eye-piece  micrometer  will  be  considered. 

This  consists  of  short  lines  ruled  on  a  slip  of  glass,  every  fifth 
line  being  longer,  and  the  tenth  still  longer  than  the  others,  to 
facilitate  counting.  The  slip  is  placed  in  a  brass  frame,  and  so 
arranged  that  its  position  may  be  somewhat  changed  by  a  fine  screw 
at  one  end  of  the  frame.  Thus  mounted,  it  is  placed  through  slits 
in  the  eye-piece  just  above  the  diaphragm.     If  its  lines,  when  thus 


726 


BLOOD. 


Fig.  16.* 


placed,  are  not  sharply  defined,  the  eye-lens  of  the  eye-piece  is  un- 
screwed until  perfect  definition  is  obtained. 

The  value  of  the  divisions  of  the  eye- 
piece micrometer  will  of  course,  other  con- 
ditions being  equal,  vary  with  the  power  of 
the  objective  employed.  To  determine  their 
value  for  any  given  objective  or  combination, 
it  is  only  necessary  to  place  one  of  the  di- 
visions of  the  stage  micrometer  in  focus  on 
the  stage  of  the  instrument,  and  then  observe 
how  many  divisions  of  the  eye-piece  microm- 
eter are  covered  by  it,  bringing  the  lines  of 
the  two  scales  into  coincidence  by  means  of 
the  screw  in  the  end  of  the  eye-piece  microm- 
eter. 

For  example,  if  the  1-1 000th  of  an  inch 
of  the  stage  scale  when  examined  under,  say 
a  1-1 2th  inch  objective,  should  cover  eighteen 
divisions  of  the  eye-piece  micrometer,  then 
obviously  each  division  of  the  latter  would 
have  a  value  of  l-18,000th  of  an  inch.  If 
now  the  draw-tube  of  the  instrument  be  with- 
drawn more  or  less,  the  1-1 000th  of  an  inch 
may  be  made  to  cover  exactly  twenty  spaces 
of  the  eye-piece  scale,  when  each  division  of 
the  latter  will  represent  just  l-20,000th  of  an 
inch.  Fig.  16. 

But  it  must  be  borne  in  mind  that  this 
will  be  true  only  so  long  as  the  then  present 
conditions  are  observed.  Hence  we  should 
now  accurately  note  (1)  the  position  of  the 
draw-tube,  which  should  be  graduated ;  (2) 
the  position  of  the  eye-lens,  in  case  it  has  been 
unscrewed  to  obtain  definition  of  the  lines  of 
the  scale ;  and  (3)  the  position  of  the  screw- 
collar  of  the  objective  for  adjustment  of  thick- 

*  Although  this  drawing  is  not  strictly  accurate,  and  the  scales  are  neces- 
sarily greatly  out  of  proportion,  yet  it  will  serve  to  illustrate  the  general  prin- 
ciple of  micrometry. 


MICROSCOPIC  DETECTION   AND   DISCRIMINATION.  727 

iiess  of  cover,  the  stage-scale  being  covered  by  gla.ss  of  the  thickness 
most  likely  to  be  used  afterward  in  the  measurement  of  objects.  So, 
also,  the  position  of  the  fine-adjiistment  of  the  microscope  should  be 
noted,  and  this  should  be  practically  the  same  in  future  measure- 
ments. 

Under  objectives  of  still  higher  power  the  value  of  each  division 
of  the  eye-piece  scale  may  be  reduced  to  l-40,000th  or  l-50,000th 
of  an  inch,  or  even  less.  The  last-named  value  would  require  an 
amplification  of  about  three  thousand  diameters.  The  amplification 
of  any  given  objective  will,  of  course,  depend  much  upon  the  stand 
and  the  eye-piece  with  which  it  is  employed. 

Application. — Having  established  the  value  of  the  divisions  of 
the  eye-piece  scale  for  a  given  combination,  the  object  to  be  measured 
is  brought  into  focus  and  then  the  number  of  divisions  of  the  scale 
it  covers  read  off,  just  as  in  measuring  an  object  with  an  ordinary 
rule.  Thus,  if  under  a  micrometry  of  l-20,000th  of  an  inch  a  blood- 
corpuscle  covered  just  five  divisions  of  the  scale,  its  diameter  would 
^^  To.'oiToj  °^*  ToTOJ  ^^  ^°  n^c\\  ;  whereas  if  it  covered  eight  divisions 
its  diameter  would  be  -gu-.-fo-jj-,  or  -25V0,  of  an  inch.  In  these  read- 
ings one  of  the  long  lines  of  the  micrometer  scale  should  be  made, 
by  means  of  the  fine  screw  at  the  end  of  the  scale,  just  coincident 
with  the  margin  of  the  corpuscle,  and  the  number  of  divisions  read 
from  this  line. 

Since  the  micrometer  scale  is  amplified  by  the  power  of  the 
eye-lens  of  the  eye-piece,  each  division  may  again  be  divided  by 
the  eye  into  fractional  parts.  After  many  experiments  on  this 
point,  we  find  that  a  practised  eye,  especially  if  accustomed  to  read- 
ing minute  scales  into  tenths,  will  read  these  subdivisions  with 
very  considerable  uniformity  to  the  tenths  of  a  division.  Hence, 
if  the  whole  division  had  a  value  of  l-20,000th  of  an  inch, 
one-tenth  of  the  division  would  represent  only  l-200,000th  of  an 
inch. 

In  confirmation  of  the  close  coincidents  that  may  be  obtained  in 
readings  of  this  kind  may  be  cited  the  results  of  three  independent 
observers  in  measuring  the  1-lOOOth  inch  divisions  of  a  stage  scale, 
the  question  being,  If  the  ninth  division  of  the  scale  measures 
twenty  divisions  of  the  eye-piece  micrometer,  what  is  the  relative 
value,  under  the  same  power,  of  the  other  divisions?  The  results 
were  as  follows : 


728 


BLOOD. 


Obseevebs. 

Divisions  or  Scaie. 

1.      '     2. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

w 

M  .......  . 

H 

19.7 
19.7 
19.7 

20+ 

20 

20.1 

19.6 
19.6 
19.6 

20 
20 
20 

20 

20— 

19.9 

20— 

20 

19.9 

19.8 
19.8 
19.8 

19.6 
19.7 
19.7 

20 
20 
20 

19.6 
19.5 
19.6 

As  will  be  observed,  the  readings,  which  were  made  upon  dif- 
ferent instruments,  did  not  differ  at  most  to  exceed  the  l-200,000th 
of  an  inch. 

In  support  of  this  uniformity  might  also  be  cited  two  inde- 
pendent series  of  measurements  of  twenty  designated  blood-corpuscles 
varying  in  size,  under  a  micrometry  of  l-20,000th  of  an  inch,  from 
6.6  to  5.0  divisions  (l-3030th  to  l-4000th  of  an  inch),  in  which  the 
results  for  each  corpuscle  were  identical  except  in  four  instances,  and 
in  each  of  these  the  discrepancy  was  only  0.1  division. 

In  order  to  ascertain  to  what  extent  the  results  might  vary  under 
different  powers  within  a  certain  range,  and  by  different  methods  of 
measurement,  seven  human  blood-corpuscles,  gradually  varying  in 
size  from  about  the  largest  to  the  smallest  found  in  this  blood,  were 
selected.  These  were  measured  under  powers  ranging  from  1150  to 
about  3500  diameters,  with  widely  difierent  values  of  the  microm- 
eter; and  also  by  the  cobweb  micrometer,  and  by  the  camera.  The 
averages  of  the  seven  corpuscles  under  these  various  measurements 
ranged  from  l-3224th  to  (by  the  camera)  l-3275th  of  an  inch,  the 
mean  of  the  averages  being  l-3236th  of  an  inch.  A  subsequent  and 
independent  measurement  of  the  same  corpuscles  by  Dr.  J.  G.  Rich- 
ardson with  a  cobweb  micrometer  gave  an  average  of  l-3266th  of  an 
inch,  the  difference  between  this  and  the  former  final  average  being 
something  less  than  l-350,000th  of  an  inch. 

2.  Average  Size  of  Mammaliak  Coepuscles. 

Repeated  experiments  of  our  own  have  shown,  as  stated  by  sev- 
eral.observers,  that,  as  a  general  result,  the  blood-corpuscles  on  dry- 
ing in  very  thin  layers  on  a  glass  slide  undergo  no  appreciable  change 
in  diameter.  When  they  have  once  attached  themselves  by  their 
flattened  sides  to  the  glass,  they  remain  unchanged  for  at  least  many 
years. 

Distribution  for  Measurement. — It  requires  some  little  experience 


MICROSCOPIC  DETECTION   AND   DISCRIMINATION.  729 

properly  to  distribute  the  corpuscles  for  measurement ;  and  various 
metliods  liiive  hoeii  advised  for  this  purpose.  A  very  j^ood  method 
is  to  moisten  a  small  conical  roll  of  soft  paper  having  a  free  end 
with  the  blood,  and  then  draw  this  over  the  slide.  The  best  method 
yet  proposed,  however,  according  to  our  experience,  is  that  of  Prof. 
Christopher  Johnston,  of  Baltimore.  This  consists  in  applying  a 
little  of  the  blood  to  the  well-ground  end  of  a  slide,  and  then  drawing 
the  latter,  slightly  inclined,  over  the  face  of  another  slide  or  over  a 
thin  glass  cover.  In  this  way  the  corpuscles  may  be  very  evenly 
distributed,  with  rarely  any  change  of  their  form  and  very  few  l)eing 
in  actual  contact.  If  the  preparation  is  for  permanent  mounting,  the 
blood  should  be  spread  upon  a  thin  glass  cover. 

If  on  examining  the  slide  with  the  microscope  any  notable 
number  of  the  corpuscles  should  be  of  irregular  form  or  have 
crenated  edges,  the  slide  should  be  rejected  for  standard  measure- 
ment. Sometimes  these  irregularities  will  be  observed  only  in  por- 
tions of  the  deposit.  But  even  when  no  such  change  in  form  is 
apparent,  the  corpuscles  sometimes  diminish  to  a  marked  extent  in 
diameter  before  becoming  dry,  especially  in  a  moist  atmosphere.  In 
no  case  should  the  measurement  of  a  corpuscle  of  irregular  form  be 
accepted  :  so  soon  as  it  has  changed  in  this  respect  it  is,  of  course,  no 
longer  normal. 

Uniformity  in  Size. — Some  years  since,  Prof.  Schmidt  announced 
that  at  least  from  95  to  98  per  cent,  of  the  corpuscles  of  the  same 
animal  were  equal  in  size ;  and  this  statement  is  frequently  repeated 
at  the  present  day.  To  what  extent  they  appear  of  the  same  size, 
however,  will  depend  much  upon  the  power  under  which  they  are 
examined.  On  the  other  hand,  it  is  sometimes  loosely  asserted  that 
the  corpuscles  of  man  vary  from  l-2000th  to  1 -4000th  of  an  inch 
in  diameter,  imjilying,  apparently  at  least,  that  there  is  but  little 
uniformity  in  this  respect. 

In  regard  to  the  extent  of  this  uniformity  in  the  corpuscles  of 
human  blood,  the  following  series  of  observations  may  be  cited. 

(1)  On  a  well-spread  slide  of  human  blood  five  hundred  corpus- 
cles were  measured  in  the  order  presented  by  a  mechanical  stage,  under 
a  power  of  2300  diameters  and  a  micrometry  of  l-40,000th  of  an  inch, 
every  corpuscle  of  normal  form  being  included. 

The  averages  of  this  series  hj  fifties  and  then  by  hundreds,  in  the 
order  measured,  ranged  as  follows : 


730 


BLOOD. 


Averages. 

Maximum. 

Minimum. 

Difference. 

By  fifties     .     . 
"   hundreds  . 

l-3213th  inch. 
l-3222d      " 

l-3292d   inch. 
1-32 74th    " 

1-1 33,880th  inch. 
l-202,862d      " 

Of  the  five  hundred  corpuscles : 

385,  or  77.0  per  cent.,  measured  from  l-3077th  to  l-3389th  of  an  inch. 

42,  "     8.4        "  "  "  l-3389th   "   l-3636th      "         " 

20,  "    4.0        "  "  "  l-3636th   "    l-4000th     "         " 

49,  "     9.8        "  "  "  l-3077th    "   l-2898th      "         " 

4,  "     0.8        "  "  "  l-2898th    "   l-2817th      "         " 

The  mean  average  of  the  five  hundred  corpuscles  was  l-3255th 
of  an  inch.  Only  one  corpuscle  in  the  series  measured  over  l-2857th 
of  an  inch,  and  only  two  less  than  l-3846th  of  an  inch,  in  diameter. 
Two  hundred  and  seventy  of  the  corpuscles,  or  64  per  cent.,  fell  in 
size  within  a  range  of  l-50,000th  of  an  inch. 

(2)  A  second  like  series,  from  a  different  sample  of  human  blood, 
examined  under  a  power  of  1150  diameters  and  a  micrometry  of 
l-20,000th  of  an  inch,  gave  the  following  results : 


Averages. 

Maximum. 

Minimum. 

DifferencG. 

By  fifties      .     . 
"  hundreds    . 

l-3215th  inch. 
l-3228th    " 

l-3275th  inch. 
l-3265th      " 

l-175,485th  inch. 
l-284,850th      " 

Of  these  five  hundred  corpuscles : 

361,  or  72.2  per  cent.,  ranged  from  l-3077th  to  l-3389th  of  an  inch. 

56,  "  11.2        "  "  "      l-3389th  "    l-3636th     "        " 

12,  "     2.4       "  "  "      l-3636th  "   l-4000th     "        " 

65,  "  13.0        "  "  "      l-30r7th  "   l-2898th     "        " 

6,  "     1.2        "  "  "      l-2898th  "   l-2817th     "        " 

The  mean  average  of  the  five  hundred  corpuscles  was  l-3242d  of 
an  inch.  Only  one  of  the  corpuscles  measured  over  l-2857th  and 
only  one  less  than  l-3846th  of  an  inch  in  diameter.  Three  hundred 
of  the  corpuscles,  or  60  per  cent.,  fell  within  a  range  of  l-50,000th 
of  an  inch. 

(3)  A  third  sample  of  similar  blood,  mounted  by  Prof.  C.  Johns- 
ton and  being  thirteen  months  old,  examined  under  a  micrometry 
of  l-40,000th  of  an  inch,  gave  as  follows  : 


MICROSCOPIC   DETECTION   AND   DISCRIMINATION.  731 


AVXBAOES. 

Maximum. 

Miaimum. 

DllTereDce. 

By  fifties     .     . 
'•     huiKlrods   . 

l-3225th  inch. 
l-3236th     " 

l-3332d  inch, 
l-330Cth     " 

l-in0,427th  inch. 
l-152,83lBt      " 

Of  the  five  hundred  corpuscles : 

406,  or  81.2  per  cent.,  ranged  from  l-3077th  to  l-33S9th  of  an  inch. 

59,  "  11.8      "  "  "       l-33S9th  "  l-3636th     "         " 

9,  "     1.8      "  "  "       l-3636th  "  l-4000th     "         " 

22,  «     4.4      "  "  "      l-3077th  "  l-2898th     "         *' 

4,  "     0.8      "  "  "       l-289Sth  "  l-2758th     "         " 

The  mean  average  of  the  five  hundred  corpuscles  was  l-3266th 
of  an  inch.  Again  only  one  corpuscle  was  found  over  l-2857th 
and  oiu  le.ss  than  l-3846tli  of  an  inch  in  diameter.  Three  hundred 
and  nine  of  the  corpuscles,  or  61.8  per  cent.,  fell  within  a  range  of 
l-50,000th  of  an  inch.  Twenty-one  of  this  series,  or  4.2  per  cent., 
measured  over  l-3000th,  and  nine,  or  1.8  per  cent.,  less  than  l-3636th 
of  an  inch. 

The  mean  average  of  tlie  three  foreo-oing;  series  of  measurements 
is  l-3254th  of  an  inch.  Of  some  twenty  other  less  extended  series 
of  measurements  of  human  blood,  the  mean  average  was  slightly 
greater  than  that  just  stated.  So  long  ago  as  1718,-  Jurin  estimated 
the  human  corpuscles  to  be  l-3240th  of  an  inch  in  diameter.  [Heuo- 
soji's  Works,  note  by  Gulliver,  216.) 

We  have  repeatedly  seen  slides  of  human  blood  in  which  no 
corpuscles  were  found  of  less  diameter  than  about  l-3600th  of  an 
inch.  On  the  other  hand,  not  unfrequently  the  corpuscles  on  dif- 
ferent slides  of  the  same  blood,  or  even  in  certain  portions  of  the 
same  slide,  are  uniformly  smaller  in  size'  than  usually  found  in  the 
given  blood.  This  diminution  in  size  in  human  blood  may  be  so 
general  that  very  many  of  the  corpuscles  measure  from  l-3600th 
to  l-4000th  of  an  inch,  or  even  less,  in  diameter.  This  contraction, 
as  already  stated,  is  likely  to  occur  when  the  blood  absorbs  moisture 
before  drying.  There  is  strong  reason  to  believe  that  the  corpuscles 
as  they  circulate  in  the  healthy  blood  are  even  more  uniform  in  size 
than  our  measurements  would  seem  to  indicate. 

Although  the  blood-disks  may  thus  under  certain  conditions 
diminish  in  size,  they  never  increase,  while  under  examination,  above 
their  normal  diameters.    Thus,  then,  whilst  the  blood  of  man  might. 


732  BLOOD. 

on  account  of  contraction  in  diameter  of  the  corpuscles,  be  con- 
founded with  that  of  an  animal  having  markedly  smaller  corpuscles, 
the  reverse  could  never  take  place.  The  importance  of  this  fact  in 
certain  medico-legal  inquiries  is  quite  apparent. 

Notwithstanding  the  possible  diminution  in  the  size  of  the  cor- 
puscles, the  general  coincidence  in  the  measurements  of  the  same 
kind  of  blood  by  different  observers  and  under  different  conditions 
is  in  the  main  very  close.  This  close  coincidence  in  the  case  of 
human  blood  under  different  circumstances  we  have  already  seen  ; 
and  equally  concordant  results  might  be  cited  of  the  measurements 
of  the  blood  of  various  animals.  For  measurements  of  this  kind, 
when  the  ordinary  eye-piece  micrometer  is  employed,  a  micrometry 
of  l-20,000th  of  an  inch  is  quite  as  satisfactory  as  a  higher  power. 

In  Disease. — It  has  long  been  known  that  in  certain  diseases 
there  is  more  or  less  change  in  the  proportion  of  the  blood-con- 
stituents; but  according  to  more  recent  observers  the  corpuscles 
themselves  may  sometimes  be  altered  in  size.  In  leucocyihcemia,  as 
already  stated,  the  white  corpuscles  are  very  greatly  increased  in 
number,  whilst  the  colored  disks  are  somewhat  diminished  in  num- 
ber, but  there  is  little  or  no  change  in  the  mean  diameter  of  the 
corpuscles. 

In  chronic  ancemia,  according  to  Hayem,  as  cited  by  Dr.  Gamgee 
[Physiological  Chemistry,  i.  148),  the  red  corpuscles  are  always  dimin- 
ished both  in  number  and  in  size,  their  average  diameter,  it  is  said, 
being  sometimes  so  low  as  l-3900th  of  an  inch ;  whilst,  according 
to  Dr.  Eichhorst,  in  progressive  pernicious  ancemia  the  corpuscles 
are  somewhat  increased  in  size,  their  mean  diameter  being  about 
l-3000th  of  an  inch. 

From  an  extended  series  of  experiments  on  different  animals,  M. 
Manassein  concluded  that  the  corpuscles  were  diminished  in  size  in 
septicsemic  poisoning,  by  a  high  temperature,  and  by  carbonic  acid 
gas;  whilst  they  were  enlarged  under  the  action  of  oxygen  and 
agents  lowering  the  temperature  of  the  body,  as  alcohol  and  quinine, 
and  in  acute  anaemia.     {Centralblatt  f.  Med.  Wiss.,  1871,  689.) 

In  the  following  table  of  the  average  size  of  the  normal  blood- 
corpuscles  of  different  animals,  our  own  measurements  were  made  in 
some  instances  while  the  blood  was  still  fluid,  but  generally  only 
after  the  corpuscles  had  dried  in  very  thin  layers.     The  average  in 


AVERAGE  SIZE  OF   RED   CORPUSCLES. 


73;J 


each  case,  expressed  in  vulgar  fractions  of  tin  En<;lish  inch,  is  the  mean 
of  two  or  more  series  of  nieasiirenients,  and  in  some  instances  of  the 
blootl  of  different  intlividuals  of  the  species.  The  powers  employed 
were  usually  1150  and  2300  diameters.  To  our  own  measurements 
we  have  added  the  corresponding  results,  with  some  additional,  of 
Prof.  Gulliver,  from  his  very  extended  measurements  as  published 
in  the  Proceedings  of  the  Zoological  Society  of  London,  June  15, 1875  ; 
and  also  in  Hewson's  Works,  p.  237  et  seq. 

Average  Size  of  the  Red  Blood- Corpuscles. 


Man 1-3250 

Monkey 1-3382 

Opossum 1-3145 

Guinea-pig  ....  1-3223 

Kangaroo    ....  1-3410 

Musk-rat     ....  1-3282 

Dog 1-3561 

Rabbit 1-3653 

Rat 1-3652 

Mouse 1-3743 

Pig 1-4268 

Ox 1-4219 

Horse 1-4243 

Cat 1-4372 

Elk 1-4384 

Buffalo 1-4351 

Wolf  (prairie)  ...  1-3422 

Bear  (black)    ...  1-3656 

Hyena 1-3644 

Squirrel  (red)  .     .     .  i   1-4140 

Raccoon j  1-4084 

Elephant     ....  1-2738 

Leopard !   1-4390 

Hippopotamus      .     .  '   1-3560 


Wormley. 


Gulliver. 


1-3200 
1-3412 
1-3557 
1-3538 
1-3440 
1-3550 
1-3532 
1-3607 
1-3754 
1-3814 
1-4230 
1-4267 
1-4600 
1-4404 
1-3938 
1-4586 
1-3600 
1-3693 
1-3735 
1-4000 
1-3950 
1-2745 
1-4319 
1-3429 


Rhinoceros    .... 

Tapir 

Lion 

Ocelot 

Mule 

Ass 

Ground-squirrel      .     . 

Bat 

Sheep  

Ibex 

Goat 

Sloth 

Platypus  (duck-billed) 

Whale ^. 

j  Capybara      .     .     .     . 

I  Seal 

!  Woodchuck  .     .     .     . 

Musk-deer     .     .     .     . 

Beaver      

Porcupine      .     .     .     . 
f  long  diam.    . 
^  I  short    " 
f  long  diam. 
short     " 


Wonnley.|  Gulliver. 


1-3649 
1-4175 
1-4143 
1-3885 
1-3760 
1-3620 
1-4200 
1-3966 
1-4912 
1-6445 
1-6189 


1-3164 


Llama 
Camel 


1-3201 
1-6408 
1-3331 
1-5280 


1-3765 
1-4000 
1-4322 
1-4220 

1-4000 

1-4175 
1-5300 

1-6366 

1-2865 

1-3000 

1-3099 

1-3190 

1-3281 

1-3484 

1-12325 

1-3325 

1-3369 

1-3361 

1-6229 

1-3123 

1-5876 


Birds. 

Wormley. 

GuUiver.           ' 

1 

Length. 

Breadth. 

Length. 

Breadth. 

1-2080 
1-1894 
1-1955 
1-1892 

1-3483 
1-3444 
1-3504 
1-3804 

1-2102 
1-2045 
1-19.37 
1-1973 
1-1836 
1-2347 
1-2005 

1-3466 

1-3598 

1-3424 

1-3643 

1-3839 

1-3470   1 

1-3369 

Turkey  

Duck 

Quail 

.     .     .    1   .     .     . 

1 

1-2140   '   1-3500 
1-1763      1-4076 

Owl 

.     .     .    1  .     .     . 

1 

1 

734 


BLOOD. 


Wormley. 


Length.      Breadth. 


Length.      Breadth. 


Tortoise  (land) 
Turtle  (green) 
Boa-constrictor 
Viper      .     .     . 
Lizard    .     .     . 


1-1250 
i-1245 


1-2200 


1-2538 


1-1252 
1-1231 
1-1440 
1-1274 
1-1555 


1-2216 
1-1882 
1-2400 
1-1800 
1-2743 


Batrachians. 

"Wormley. 

Gulliver. 

Length. 

Breadth. 

Length. 

Breadth. 

1-1089 

1-1801 

1-1 108      1-1821 

Toad 

1-1043 
1-848 
1-400 
1-363 

1-2000 
1-1280 
1-727     i 
1-615 

Triton     .          

Amphiuma  tridactyluni 

i-358 

1-622 

Fishes. 

Gulliver. 

Length. 

Breadth. 

Tront          

1-1524 
1-2099 

1-2460 

1-2S24 

Perch 

Pike 

1-2000       1-3555 
1-1745       1-2842 
Circular.    1-2134 

Eel 

1-6400 

On  comparing  the  foregoing  results  of  Prof.  Gulliver  and  our 
own,  it  is  seen  that  the  greatest  difference  is  in  the  blood  of  the 
opossum  (Didelphys  Vtrginiana),  in  which  the  difference  between 
the  averages  is  1-27,1 52d  of  an  inch.  Not  only  in  respect  to  size, 
according  to  our  own  measurements,  are  the  corpuscles  of  the  opossum 
closely  allied  to  those  of  man,  but  they  also  present  that  peculiar 
bright  appearance,  or  "stamp  of  individuality,"  as  Prof.  Johnston 
expresses  it  (Mieroscopy  of  the  Blood,  Transactions  International 
Medical  Congress,  1876,  479),  observed  in  human  corpuscles.  This 
same  peculiarity  is  also  strongly  marked  in  the  blood-corpuscles  of 
the  kangaroo. 

The  next  greatest  difference,  in  the  above  measurements,  occurs 
in  the  blood  of  the  guinea-pig,  in  which  it  is  l-36,200th  of  an  inch. 
However,  the  species  of  animal  examined  by  Prof.  Gulliver  was 


MICROSCOPIC  DISCRIMINATION.  735 

the  Cav'ia  cohaya,  whilst  that  which  we  examined  was  the  (Javia 
apcre<t.  Our  avcra<;c  of  1-3228(1  of  an  inch  is  based  on  the  measure- 
niont  of  three  hmidrod  corpuscles  of  the  same  animal.  The  mean 
diameter  of  lour  hundred  corpuscles  of  a  like  animal  measured  by 
Dr.  J.  J.  W()o(l\vai-(l  {LouimiUe  Med.  Jour.,  Aug.  1876,  120)  was 
1-321 3th  of  an  inch. 

With  the  exceptions  now  stated,  and  some  three  or  four  others  of 
minor  extent,  the  results  of  the  foregoing  series  of  measurements  are 
practically  identical.  From  repeated  measurements  of  the  blood  of 
the  dog,  Dr.  J.  J.  Woodward  concluded  that  the  corpuscles  of  this 
animal  were  more  closely  allied  in  size  to  those  of  man  than  is  usually 
stated  by  writers,  and  that  these  bloods  might  thus  readily  be  con- 
founded, even  in  their  fresh  state.  [Amer.  Jour.  Med.  Sci.,  Jan.  1875, 
151 ;  and  Louisville  Med.  Jour.,  Aug.  1876, 121.)  Our  own  average 
of  the  blood  of  the  dog  is  based  on  the  examination  of  the  blood  of 
a  number  of  animals  differing  much  in  size  and  variety,  the  results 
in  each  case  being  closely  concordant. 

The  apparent  size,  under  a  power  of  1150  diameters,  of  the 
prevailing  corpuscles  of  six  different  bloods,  embracing  the  princii)al 
range  of  mammalian  blood,  is  shown  in  Plate  XVI.  It  will  there 
be  seen  that  under  this  power  corpuscles  differing  in  diameter  by  the 
1-1 00,000th  of  an  inch  are  readily  discriminated^  The  corpuscles 
as  they  appeared  to  the  eye  under  a  simple  lens  amplifying  184  times 
were  figured  by  Hewson,  he  representing  those  of  man,  the  dog,  and 
the  rabbit  of  the  same  size,  and  those  of  the  ox,  cat,  mouse,  ass,  and 
bat  of  equal  size.     [Uewson's  Woi^Jcs,  217.) 

From  a  series  of  microscopic  measurements  of  the  blood-corpus- 
cles, C.  Schmidt,  in  1848,  claimed  that  in  this  manner  the  blood  of 
many  of  the  mammalia  could  be  distinguished  from  that  of  man 
and  he  proposed  the  method  for  the  diagnosis  of  suspected  stains  in 
criminal  cases.  His  measurements  were  made  with  a  power  of  500 
diameters,  and  in  each  blood  he  took  the  average  of  forty  corpuscles. 
His  results  correspond  for  the  most  part  quite  closely  with  the 
measurements  already  given. 

Limit  of  Discrimination. — The  difference  thus  found  to  exist  in 
the  average  size  of  the  corpuscles  of  mammalian  blood  enables  the 
microscopist  to  discriminate  readily  the  blood  of  certain  animals, 
including  man,  from  that  of  certain  other  animals  of  this  class, 
especially    when,    as  strongly   advised   by   Dr.   J.   G.    Richardson 


736  BLOOD. 

{Amer.  Jour.  Med.  SgL,  July,  1874,  102),  the  higher  powers  of  the 
instrument  are  employed. 

Thus,  for  example,  if  it  were  claimed,  as  in  a  case  some  years 
since,  that  a  blood  was  that  of  a  rabbit,  and  under  examination  the 
corpuscles  were  found  to  have  an  average  diameter  of  about  l-3300th 
of  an  inch,  it  would  be  quite  certain  that  the  blood  was  not  that  of 
a  rabbit.  But  the  fact  that  the  corpuscles  had  a  mean  diameter  of 
about  l-3300th  of  an  inch  would  not  in  itself  prove  that  the  blood 
was  that  of  man,  since  the  result  would  be  equally  consistent  with 
the  blood  of  several  different  animals.  So,  on  the  other  hand,  if  the 
mean  diameter  of  the  corpuscles  was  found  to  be  about  l-3700th  of 
an  inch,  this  fact  alone  would  not  prove  that  the  blood  was  that 
of  a  rabbit,  since  it  might  be  that  of  certain  other  animals,  or  even, 
under  certain  conditions,  the  blood  of  man.  How  far  a  discrimina- 
tion of  this  kind  could  in  any  given  case  be  safely  carried  would 
depend  much  upon  the  number  and  the  range  in  size  of  the  corpus- 
cles measured. 

This  difficulty  of  individualization  arises  from  the  fact,  as  we 
have  already  seen,  that  the  average  diameters  of  the  corpuscles  of 
the  different  mammals  are  in  many  instances  at  least  practically  the 
same,  and  these  averages,  for  the  most  part,  pass  by  imperceptible 
gradations  throughout  the  entire  class.  Thus,  virtually  of  the  same 
size  as  the  corpuscles  of  man  are  at  least  those  of  the  guinea-pig, 
musk-rat,  seal,  beaver,  opossum,  and  capybara,  whilst  those  of  certain 
other  animals  are  but  slightly  larger  and  might  be  reduced  in  size  to 
those  of  man. 

Hence,  then,  the  microscope  may  enable  us  to  determine  with  great 
certainty  that  a  blood  is  not  that  of  a  certain  animal  and  is  COi^- 
siSTENT  toith  the  blood  of  man;  but  in  no  distance  does  it,  in  itself, 
enable  tis  to  say  that  the  blood  is  really  human,  or  indicate  from  what 
particular  species  of  animal  it  was  derived. 

There  seems  to  be  much  misunderstanding  as  to  the  true  value 
of  this  instrument  in  investigations  of  this  kind,  it  being  regarded 
by  some  as  nearly  or  altogether  useless  for  this  purpose,  whilst  others 
claim  for  it  results  wholly  at  variance  with  the  facts  in  the  case. 
This,  like  many  other  tests,  has  its  fallacies,  and  if  these,  in  a  given 
case,  cannot  be  reasonably  met,  the  accused  should  have  the  benefit 
of  the  doubt. 


IN    nRIED    8TATE.  737 

V.  Examination  of  Dried  Blood. 

For  the  recovery  of  the  blood-corpuscleji  i'voiw  dried  stains  and 
coan'iihi  various  solutions  and  liquids  have  been  advised.  Of  these 
may  be  uientioned  sodium  chloride  and  sulphate,  potassium  iodide, 
arsenious  acid,  corrosive  sublimate,  and  diluted  glycerine.  So,  also, 
Moleschott  recommended  a  33  per  cent,  solution  of  pota.ssiura  hy- 
drate; and  Prof.  Rednevv,  of  St.  Petersburg,  a  solution  of  two  parts 
of  potassium  dichromate  with  one  part  of  sodium  sulphate  in  one 
hundred  parts  of  water.  Pacini's  fluid,  which  has  been  highly  ex- 
tolled for  this  ])urpose,  consists  of  a  mixture  of  common  salt,  cor- 
rosive sublimate,  glycerine,  and  water. 

After  considerable  experience  with  most  of  these  liquids  for  this 
purpose,  and  others,  side  by  side  with  jjure  water,  we  prefer,  at  least 
in  most  instances,  the  latter  fluid,  added  in  quantity  not  to  exceed 
the  proportion  present  in  normal  blood.  A  solution  of  glycerine,  of 
sp.  gr.  1030,  generally  answers  the  purpose  very  well,  and  has  the 
advantage  of  not  evaporating  as  readily  as  pure  water.  When  the 
stain  is  quite  old,  the  addition  of  a  little  potassium  hydrate  may 
much  facilitate  the  disintegration  of  the  mass. 

For  the  examination  it  is  much  more  satisfactory,  as  already 
stated,  to  have  a  dried  clot,  even  if  exceedingly  minute,  than  to 
employ  a  portion  of  stained  fabric.  Even  in  only  a  minute  stain  a 
clot  may  generally  be  found  by  examining  it  under  a  simple  lens. 
Any  clot  thus  found  is  placed  on  a  glass  slide,  gently  crushed,  moist- 
ened with  a  small  drop  of  water,  then  covered  with  a  thin  glass 
and  examined  in  the  usual  manner.  In  the  absence  of  a  clot,  the 
scrapings  or  a  few  fibres  of  the  stained  fabric  are  examined  in  a 
similar  manner. 

When  the  stain  is  at  least  comparatively  fresh,  the  corpuscles  may 
manifest  themselves  very  quickly ;  whilst  if  the  mass  is  old,  it  may 
require  some  hours  for  disintegration.  In  this  respect,  however, 
great  differences  may  be  observed  even  in  stains  of  the  same  age. 
The  breaking  up  of  the  mass  is  sometimes  much  hastened  by  gently 
moving  the  glass  cover.  When  the  corpuscles  are  slow  to  separate, 
it  is  more  satisfactory  to  w^atch  the  disintegration  under  a  medium 
power,  as  a  one-fifth  inch  objective,  and  as  they  appear  measure  them 
under  a  higher  power.  A  very  good  method  of  examining  old  stains 
is  to  place  the  moistened  clot  on  the  thin  glass  and  then  invert  this 
over  a  glass  slide  having  a  slightly  concaved  centre. 

47 


738 


BLOOD. 


If,  during  the  examination,  any  of  the  corpuscles  become  entirely 
decolorized  and  spherical  in  form,  they  should  not  be  included  in  the 
measurements,  since  they  -are  obviously  no  longer  normal.  Some  of 
the  corpuscles,  as  already  mentioned,  resist  the  action  of  water  much 
more  than  others.  In  fact,  these  are  the  corpuscles  generally  seen  in 
examinations  of  this  kind. 

Experiments. — In  order  to  ascertain  how  far  the  blood-corpuscles 
of  different  animals  might  be  recovered  of  their  normal  size  from 
dried  blood  after  various  periods,  the  following  examinations  were 
made,  the  dried  blood  being  either  in  the  form  of  a  stain  on  muslin 
or  as  dried  coagula  that  had  been  loosely  preserved  in  paper.  To 
these  average  measurements  are  added  those  of  the  corresponding 
blood  as  obtained  from  the  fresh  fluid,  or  the  blood  after  drying  in 
thin  layers  on  a  glass  slide.  In  every  instance,  save  one,  not  less 
than  forty  corpuscles  were  measured. 


Examination  of  Old  Blood-Stains. 


Animal. 

Age  of  Stain. 

Eemarks. 

i          Average. 

Fresh  Blood. 

(1)  Human     .     . 

2  months  old. 

Stain,  unknown. 

1 
l-3358th  inch. 

l-3250th  inch. 

(2)        "           .     . 

2i     " 

Stain. 

l-3236th     " 

ti           It 

(3)        "           .     . 

3       " 

" 

i   l-3384th     " 

<i            11 

(4)        "           .     . 

19     " 

Clot. 

l-3290th     " 

11            ii 

(5)  Elephant  .     . 

13     " 

cc 

l-2849th     " 

l-2738th     " 

(6)  Dog      .     .     . 

4       '<         i< 

Trace   of    stain, 
unknown. 

l-3626th     " 

l-3561st      "      ! 

(7)  Rabbit      .     . 

18     "          " 

Clot. 

1  l-3683d      " 

l-3653a      "       i 

(8)0x   .     .     .     . 

16     " 

Stain. 

!   l-4544th     " 

l-4219th     " 

(9)    "•     .     .     .     . 

32     "          " 

Stain,  unknown. 

l-4495th     " 

"           " 

(10)    "     .     .     .     . 

4i  years     " 

Clot. 

l-4535th     " 

((           li      1 

(11)  Buffalo      .     . 

18  months" 

(( 

l-4312th     " 

1-43  5 1st     " 

(12)  Goat    .     .     . 

17        "        " 

Stain. 

l-5897th     " 

l-6189th     " 

(13)  Ibex     .     .     . 

18        "       " 

Clot. 

l-6578th     " 

1-6445 th     " 

In  the  case  of  the  human  blood,  No.  1,  two  months  old,  the  deposit  was  in  the  form  of  a 
thin  stain  on  muslin,  and  its  nature,  other  than  that  it  was  mammalian  blood,  was  unknown 
at  the  time  of  examination.  The  corpuscles  were  readily  found,  and  two  series  of  thirty 
corpuscles  each  were  measured.  In  the  human  blood  two  and  a  half  months  old,  fifty 
corpuscles,  ranging  from  l-3125th  to  l-3448th  of  an  inch,  were  measured. 

The  blood-stain  of  the  dog,  No.  6,  was  prepared  by  Dr.  Frankenberg,  and  consisted  of 
a  single  stain  so  minute  as  to  be  barely  visible  to  the  naked  eye  :  its  nature  at  the  time  of 
the  examination  was  unknown.     In  this  instance  only  fifteen  corpuscles  were  measured. 

In  the  ox  blood  four  and  half  years  old,  the  corpuscles  were  rather  readily  obtained, 
and  two  closely  concordant  series  of  measurements  were  made. 

In  examinations  of  this  kind  it  should  be  borne  in  mind  that  certain  portions  of  a 
deposit  may  fail  to  yield  satisfactory  results,  whilst  from  other  portions  the  corpuscles  may 
be  readily  obtained. 


EXAMINATION    IN    DIMKD    STATK.  T-VJ 

Cases. — In  ;i  case  ol"  murder  in  \vlii(;li  we  were  consulted  some 
years  siiici'  [Sfatc  of  Ohio  v.  John  Jhirck/ci/),  ujjon  llio  pantaloons 
oi'  ti)e  prisoner  a  slain  tliat  a|iparc'ntly  Iiad  hocn  wjuslicd  WiLs  found; 
but  the  linen  of  the  j)o{!kt't  iininediately  under  the  stain  exhibited  a 
marlxed  stain,  frotn  which  minute  clots  were  ol>tained.  These  readily 
revealed  tiie  presence  of  blood-corpuscles  ranging  in  diameter  from 
l-3030th  to  l-3600th  of  an  inch,  the  average  being  l-3242d  of  an 
inch.  Before  execution  the  prisoner  admitted  that  he  had  hastily 
washed  the  stain  with  water  from  a  small  stream  near  which  the 
murder  was  committed. 

In  another  case,  it  was  claimed  that  some  spots  upon  a  hat  were 
made  by  the  blood  of  a  turkey,  and  was  so  testified  by  two  associates 
of  the  accused.  The  blood,  however,  was  clearly  that  of  a  mammal, 
and  was  quite  consistent  with  that  of  the  human  subject.  In  both 
these  instances  the  examination  was  made  within  a  few  days  after  the 
stain  was  received. 

In  a  case  tried  a  few  years  since,  the  clothes  of  the  accused  pre- 
sented a  great  number  of  stains,  some  of  which  were  quite  large, 
which  he  claimed  were  due  to  the  slaughter  of  sheep,  his  statement 
in  regard  to  killing  sheep  being  confirmed  by  several  witnesses.  A 
closer  examination  of  the  clotlfes,  however,  indicated  a  somewhat 
marked  difference  between  certain  of  the  stains,  -and  independent 
examinations  by  three  different  observers  showed  that  while  some 
of  the  stains  contained  blood-corpuscles  quite  consistent  with  those 
of  the  sheep,  others  contained  corpuscles  wholly  inconsistent  with 
those  of  that  animal,  but  quite  consistent  with  human  blood. 

Fallacies. — In  the  examination  of  suspected  stains  the  examiner 
should  bear  in  mind  the  possible  presence  of  vegetable  spores,  which 
in  appearance  and  size  may  closely  resemble  blood-corpuscles.  Two 
instances  of  this  kind  have  come  within  our  own  personal  knowledge. 

In  one  of  these,  minute  circular  bodies  were  found  in  very  great 
numbers  in  a  suspected  pail  partly  filled  with  water,  and,  as  many  of 
the  bodies  had  a  diameter  of  about  l-3300th  of  an  inch,  they  were 
pronounced  human  blood-corpuscles.  A  subsequent  and  independent 
examination,  however,  proved  them  to  be  simply  the  sporules  of  a 
confervoid  algae. 

In  a  more  recent  case,  similar  spores,  found  in  a  suspected  de- 
posit upon  a  rock,  were  at  first  mistaken  for  blood-corpuscles;  but  a 
subsequent  examination  convinced  the  observer  tiiat  he  was  in  error. 


740  BLOOD. 

Gorup-Besanez  cites  a  similar  case  iPhys.  Chem.,  1867,  350),  where 
an  earth  which  from  its  red  color  appeared  strongly  saturated  with 
blood  was  found  on  microscopic  examination  by  Prof.  Erdmann  to 
contain  circular  bodies  which  at  first  might  readily  be  mistaken  for 
blood-corpuscles,  but  which  were  really  the  spores  of  the  algse  Por- 
phyridium  cruentum. 

The  general  character  and  appearance  of  spores  of  this  kind, 
when  more  carefully  examined,  will  in  most  instances  readily  dis- 
tinguish them  from  blood-corpuscles ;  they  usually  vary  much  more 
in  size  than  the  corpuscles  of  any  single  blood :  in  respect  to  size, 
however,  they  may  be  pretty  uniform.  Under  the  action  of  water 
they  generally  remain  unchanged  in  appearance ;  whereas  blood- 
corpuscles  become  transparent  and,  at  least  for  the  most  part,  dis- 
appear from  view.  It  need  hardly  be  stated  that  vegetable  spores 
have  not  the  chemical  and  optical  properties  of  blood-corpuscles. 

Location  of  Stains. — jSTot  only  should  all  stains  of  this  kind  be 
accurately  located  upon  the  article  on  which  they  are  found,  but  it  is 
sometimes  of  very  great  importance  to  determine  upon  which  side  of 
the  fabric  they  were  received.  For  determinations  of  this  kind  the 
binocular  microscope,  with  a  low  power,  will  sometimes  be  found  very 
useful.  The  following  very  remarkable  case  {State  of  Ohio  v.  Amelia 
Richardson,  1876),  in  which  this  question  was  involved,  may  be  briefly 
cited. 

Two  pistol-shots  were  heard  shortly  after  midnight,  at  an  interval 
of  several  minutes  or  more.  A  few  minutes  after  the  second  shot 
an  officer  entered  the  room  from  which  the  report  proceeded.  He 
found  a  man  lying  on  the  floor  on  the  left  side  of  the  bed,  dead, 
with  a  pistol-ball  wound  in  his  head  and  blood  oozing  from  the 
wound  upon  the  carpet.  The  wife  of  the  dead  man  was  bleeding 
from  an  incised  wound  in  the  throat,  and  was  also  wounded,  appar- 
ently by  a  ball,  in  the  loose  flesh  upon  her  side,  upon  which  there 
were  two  apertures  near  each  other. 

The  woman  stated  that  while  asleep  her  husband  attempted  to 
cut  her  throat  with  a  razor,  which  she  wrested  from  him.  He  then 
shot  her  in  the  side,  after  which  she  obtained  the  pistol  and  shot 
him  in  self-defence.  In  confirmation  of  her  statement  she  pointed 
to  blood-stains  on  the  upper  portion  of  the  sheet  on  the  right  side 
of  the  bed,  which  side  she  claimed  she  occupied  when  she  received 
the  wound  in  her  throat. 


IX    TXSECTS.  741 

On  carefully  examining  these  stains,  they  were  readily  found  to 
consist  of  blood.  But  on  one  side  of  the  sheet  the  stains  were  much 
more  marked  than  on  the  other,  and  they  contained  many  small 
clots;  whilst  on  the  least  stained  side  there  were  but  few  clots,  and 
these  were  very  minute ;  further,  i)ortions  of  the  stains  at  their 
edges,  on  the  most  strongly  marked  side  of  the  sheet,  did  not  fully 
extend  through  the  fabric.  These  apjaearances,  with  other  facts, 
seemed  clearly  to  indicate  that  the  blood  was  received  on  the  side  of 
the  sheet  on  which  the  stains  were  most  marked.  This  proved  to  be 
the  under  side  of  the  lower  sheet  as  found  on  the  bed. 

At  the  trial  of  the  case,  the  State  held  that  the  woman  first  shot 
her  husband  upon  the  left  side  of  the  bed,  aud  that  his  body  then  fell 
or  was  put  upon  the  floor,  and  that  the  sheet  which  was  thus  stained 
was  then  reversed  so  as  to  bring  the  stains  upon  her  side  of  the  bed. 
Several  surgeons  testified  that  in  their  opinion  the  wound  on  the 
throat  of  the  woman  was  self-inflicted,  and  that  when  the  ball  was 
received  upon  her  side  the  skin  was  folded  and  distended.  There 
was  strong  reason  to  believe  she  had  an  accomplice,  who  escaped 
from  the  house  as  the  officer  entered.  The  woman  was  found  guilty 
of  murder  in  the  second  degree. 

Blood  in  Insects. — The  singular  observation  has  been  made  by 
M.  Curtmann  that  when  blood-sucking  insects  are  killed  stains  may 
result  in  which  human  blood-corpuscles  are  plainly  recognizable. 
Human  blood,  he  states,  is  more  rapidly  digested  by  bugs  than  by 
mosquitoes,  since  it  is  not  detected  in  the  former  after  twelve  hours, 
while  in  the  latter  it  may  be  found  even  later  than  twenty-four  hours 
after  the  ins^estion  of  the  blood. 


PLATE   I. 


Fig.  1.  3-^0  grain   Potassium   Oxide,  as  nitrate  or  chhride, -\- Platinic 

Chloride,  X  225  diameters. 
"    2.  y^Q-  grain  Potassium  Oxide,  as  nitrate,  +  lartaric  Acid,  X  100 

diameters. 
"    ^-  2TT  g'^^i"  Potassium  Oxide,  as  chloride,  +  Sodium  Tartrate,  X  80 

diameters. 
"    4.  2-^-o  grain    Potassium    Oxide,   as   nitrate,  +  Picric   Acid,  X  40 

diameters. 
"     5.  yi^  grain  Ammonia,  as  ammonium  chloride,  -|-  Picric  Acid,  X  40 

diameters. 
"     ^-  TS"  g^^i"!  Sodium  Oxide,  +  Picric  Acid,  X  40  diameters. 


Il.l.l 


/;,/ 


nn 


PLATE  11. 


Fig.  1.  -^-T-g-jf  grain  Sodium  0:ki'D'b, -\- Potassium  Metantimoniafe,  X  1^0 

diameters. 
"     2.  ^  grain  Sodium  Oxide,  -\-  Tartaric  Acid,  X  40  diameters. 
"    ^-  nrW  grain  Sodium  Oxide,  as  chloride,  -|-  Platinic  Chloride,  X  40 

diameters. 
"    ^-  T¥T7  gJ'^i'i  Sulphuric  Acid,  -)-  Barium  Chloride,  X  100  diameters. 
"     5.   Htdbofluosilicic  Acid,  -|-  Barium  Chloride,  X  100  diameters. 
"    ^-  TOT  grain  Sulphuric  Acid,  -\-  Strontium  Nitrate,  X  75  diameters. 


Fi^f.5. 


Fiil-O- 


PLATE   III. 


Fig.  1.  Y017  grain  Hydrochloric  Acid,  +  Lead  Acetate,  X  40  diameters. 
"    2.  YWTT  grain    Oxalic    Acid,    on    spontaneous    evaporation,  X  80 

diameters. 
"     3.  -Y^  grain  Oxalic  Acid,  +  Calcium  Chloride,  X  225  diameters. 
"    ^'  T0T5"  gi"ain  Oxalic  Acid,  -(-  Barium  Chloride,  X  80  diameters. 
"    ^-  T¥Tr  grain  Oxalic  Acid,  +  Strontium  Nitrate,  X  125  diameters. 
"    ^-  7¥Tr  gi'ain  Oxalic  Acid,  -(-  Lead  Acetate,  X  80  diameters. 


111. 


/;; 


/; 


"f 


nn 


n,.y 


/;;/.// 


PLATE  IV. 


Fig.  1.  Yo^^  grain  Hydrocyanic  Acid  vapor,  -f  Silver  Nitrate,  X  225 
diameters. 

"  ■^-  1 0  0^0  0  0  gi'aiii  Hydrocyanic  Acid  vapor,  +  Silver  Nitrate.  X  1-5 
diameters. 

"  ^'  1 0^0  0  E^^^^  Phosphoric  Acid,  -j-  Ammonium  Magnesium  Sul- 
phate, X  80  diameters. 

"     4.  Tartar  Emetic,  from  hot  supersaturated  solution,  X  40  diameters. 

"     5.  Arsenious  Oxide,  sublimed,  X  125  diameters. 

"  6.  YoTT  grain  Arsenious  Oxide,  -j-  Ammonium  Silver  Nitrate,  X  75 
diameters. 


//<•/  / 


/;,/..- 


/of    ', 


'v./..-y. 


flf/.O'. 


PLATE  V. 


YlQ.  1.  Y^  grain  Arsenic  Oxide,  -\-  Ammonium   Magnesium  Sulphate, 
X  75  diameters. 
"    2.  Corrosive  Sublimate,  sublimed,  X  40  diameters. 
<'     3.  __i^  grain  Lead,  -|-  diluted  Sulphuric  Acid,  X  80  diameters. 
««     4.  _^  grain  Lead,  -f  diluted  Hydrochloric  Add,  X  80  diameters. 
"     5.   2-^L^  grain  Lead,  +  Potassium  Iodide,  X  80  diameters. 
«     6.  y^^  grain  Zinc,  -(-  Occa^^z'c  J.ctc^,  X  80  diameters. 


\hu\ 


/  ///  o 


um 


PLATE  VI. 


48 


Fig.  1.  YUT  gi'^ii  Nicotine,  -f-  Platinic  Chloride,  X  40  diameters. 

2.  yi-g-  grain  Nicotine,  -|-  Corrosive  Sublimate,  X  40  diameters. 

3.  YoVo  gi'^iii  Nicotine,  +  Picric  Acid,  X  40  diameters. 

4.  Conine,  pure,  -f-  vapor  of  Hydrochloric  Acid,  X  40  diameters. 

5.  yig-  grain  Conine,  -\-  Picric  Acid,  X  40  diameters. 

6.  Ywo  g^'^iii  Morphine,  -[-  Potassium  Hydrate,  X  40  diameters. 


n.n.vi 


//>/  / 


f'n,  y 


h.l 


/'w 


/■'/'/./' 


PLATE   VIL 


Fig.  1.  Yyg-  grain  Morphine,  -{-  Potassium  Iodide,  X  40  diameters. 

2.  y-J-Q-  grain  Morphine,  -j-  Potassium  Chromate,  X  80  diameters. 

3.  -j-^-jy  grain  Morphine,  -|-  Platinic  Cliloride,  X  80  diameters. 

4.  YCTj-  grain  Meconic  Acid,  -|-  Barium  Chloride,  X  80  diameters. 

5.  Y^  grain  Meconic  Acid,  -\-  Hydrochloric  Acid,  X  75  diameters. 

6.  Yuu  g^^iii  Meconic  Acid,  -|-  Potassium  Ferricyanide,  X  40  diam- 
eters. 


1 1,1 1.  All 


////  / 


■/// 


MM 


/;./.. 


//>/.// 


n 


PLATE   VIIL 


Fig.  1.  YTo  grain  Meconic  Acid,  +  Calcium  Chloride^  X  75  diameters. 
"     ^'  TWO  gi"ain  Narcotine,  -|-  Potassium  Hydrate,  X  40  diameters. 
"     ^-  OTT  oJ"ain  Narcotine,  -)-  Potassium  Acetate,  X  80  diameters. 
"     ^-  TW  gi"ain  Codeine,  -j-  Iodine  in  Potassium,  Iodide,  X  40  diameters. 
"    5.  ywq  grain  Codeine  Iodide,  from  alcoholic  solution,  X  75  diameters. 
"     ^-  T¥¥  grain  Codeine,  -(-  Potassium,  Sulphocyanide,  X  40  diameters. 


I.ll. 


///// 


////./-' 


nn 


Fuio 


Firf.6. 


PLATE   IX. 


Fig.  1.  Yoir  grain  Codeine,  -\-  Potassium  Dichromafe,  X  40  diameters. 
"     2.  Y^  grain  Codeine,  -(-  Potassium  Iodide,  X  40  diameters. 
«     3.  y^i^-g-  grain  Narceine,  -|-  Iodine  in  Potassium  Iodide,  X  40  diam- 
eters. 
«     4,  .g.1^  grain  Narceine,  -|-  Potassium  Dichromate,  X  40  diameters. 
"     5.   gi^.  grain  Opianyl,  -|-  Iodine  in  Potassium  Iodide,  X  40  diameters. 
«     6.    ,^Q  grain  Opianyl,  -|-  Bromine  in  Bromohydric  Acid,y^  40  diam- 
eters. 


n.H.ix 


/'./ 


5^ 


I  J        I  ^       i 


■v//../. 


Fiif.o'. 


n 


PLATE   X. 


YiQ.  1.  j^  grain  STRYCHNINE,  -f-  Potassium  Hydrate  or  Ammonia,  X  40 
diameters. 
"     2-  TW  gJ'a^'3  Strychnine,  -|-  Potassium  Sulphocyanide,  X  40  diam- 
eters. 
"     3.  -gig.  grain  Strychnine,  -j-  Potassium  Dichromate,  X  40  diameters. 
"     4.   2~5Vn-  grain  Strychnine,  -f-  Potassium  Dichromate,  X  80  diameters, 
grain  Strychnine,  -|-  Auric  Chloride,  X  40  diameters. 


1000 


6.  --^^-^  grain  Strychnine,  +  Platinic  Chloride,  X  40  diameters. 


/;. 


I'irl.O. 


nn 


PLATE   XI. 


Fig.  1.  YWW^  grain  Strychnine,  -[-  Picric  Acid,  X  80  diameters. 

"     2.  Ywo  grai'^  Strychnine,  +  Corrosive  Sublimate,  X  40  diameters. 

"  3.  ^_  grain  Strychnine,  +  Potassium  Ferricyanide,  X  40  diam- 
eters. 

"  4.  -yqw^  erain  Strychnine,  -(-  Iodine  in  Potassium  Iodide,  X  80 
diameters. 

"  ^-  Too'  grain  Brucine,  -(-  Potassium  Hydrate  or  Ammonia,  X  40 
diameters. 

"     6.  yi^  grain  Brucine,  -{-  Potassium  Sulphocyanide,  X  40  diameters. 


ll.i.-XI 


/■///  / 


/;>/../. 


/;./.// 


PLATE   XII. 


Fi(j.  1 .  -^_i_g.  grain  Brucine,  -\-  Potassium  Bichromate,  X  80  diameters. 

"     2.  y-oVs-  grain  Brucine,  -|-  Platinic  Chloride,  X  40  diameters. 

'<     3.  _-i^  grain  Brucine,  -j-  Potassium  Ferricyanide,  X  40  diameters. 

"  4.  1^  grain  Atropine,  +  Potassium  Hydrate  or  Ammonia,  X  75 
diameters. 

<■'■  5.  1^  grain  Atropine,  -)-  Bromine  in  Bromohydric  Acid,  X  75  diam- 
eters. 

«  6.  y^-^^-Q  grain  Atropine,  -\-  Bromine  in  Bromohydric  Acid,  X  125 
diameters. 


1,.t.-XII 


f'.r  / 


/v//. :/ 


J'i>r./r 


nn 


PLATE   XIII. 


Fig.  1.  Yw^  grain  Atropine,  +  Picric  Acid,  X  80  diameters. 
"     2.  yItj  grain  Atropine,  -f-  Aw-ic  Chloride,  X  80  diameters. 
"     ^-  TFO"  S^^^'^  Veratrine,  -|-  J.M?nc  CJdoride,  X  40  diameters. 
'<    4.  _i^  grain    Veratrine,  -)-  Bromine    in    Bromoliydric   Acid,  X  80 

diameters. 
"     5.  SoLANiNE,  from  alcoholic  solution,  X  80  diameters. 
"     6.  Y^  grain  Solanine,  as  sulphate,  on  spontaneous  evaporation,  X  80 

diameters. 


1.1.  XIII 


ru/.-'. 


I'n, 


////.// 


nn 


PLATE  XIV. 


49 


Fig.  1.  YTo-  grain  Morphine,-]-  Iodine  in  Potassium  Iodide,  X  40  diam- 
eters. 

"  ^-  10^0  6  g'"ai"  Morphine,  -\-  Potassium  lodohydrargyrate,  X  40  diam- 
eters. 

"     3.  Jervine,  from  ethereal  solution,  X  40  diameters. 

"    ^-  Too"  gi'^i"  Jervine,  -|-  Sulplmric  Add,  X  75  diameters. 

"     ^-  TTU"  gi'ain  Jervine,  -j-  Nitric  Acid,  X  75  diameters. 

"     6.  Jervine,  from  blood  of  cat,  X  75  diameters. 


n.iirxiv. 


I'ni  I- 


/"/ 


/>./, 


//'/ 


FhjF) 


/■'/'/.  //■ 


Mrs.T.G.Wormle)'.ad  nat.iiel.el  &culp. 


PLATE  XV. 


Fig.  1.  GrBLSEMiNE  Hydrochloride,  X  40  diameters. 
"     2.  GrELSEMic  AciD,  from  ethereal  solution,  X  40  diameters. 
"     3.  Gelsemic  Acid,  sublimed,  X  75  diameters. 
"     4.  yJ=Q^  ejrain    GtELSEMIC    Acid,  -f  Sulphuric  Acid,   then  Ammonia, 

X  75  diameters. 
"     5.   H^MATiN  Hydrochloride,  X  400  diameters. 
"     6.  H^MATiN  Hydrochloride,  from  3-J-g^  grain  blood,  X  750  diameters. 


n.iir.w 


n.f.  I. 


Fill,. 


Fhf.  d 


PLATE  XVL 


Apparent  size  of  Red  Blood  Corpuscles  under  an  amplification  of 
1150  diameters. '  The  actual  diameters  of  the  corpuscles  delineated  are 
expressed  in  vulgar  fractions  of  an  inch,  and  as  the  numerator  is  always  one, 
this  is  omitted  in  the  illustration,  thus:  3250  ^^gVo  ^^  ^^  inch. 


Fig.  1.   Blood-Corpuscles  of     Man,  X  1150  diameters;    average   g-^Vo  ^'^^^• 


'  Dog,  X 
'  Mouse,  X 
'  Ox,  X 
■  Sheep,  X 
'      Goat,  X 


u                  1            u 
356  1 

a                  1            a 

3743 

4119 

iBTO" 

u                 1           u 

llilrWl 


V 

M7S 

m 

3400  j 

"^ 

r  (^^«T( 

^  , 

r^ 

^^ 

1     V 

-^ 

^' 

^' 

f  3«00  j        1 

l^^^ 

{    3450 

)H 

r--\ 

r~\  1 

■  / 

■  '     3550 

3600  j 

—  [ 

0 

r 

(   30/5    )     J 

^^k 

^-^ 

■^v    , 

-\(3000)       ^H 

B 

bl 

3900  j(    3300  j  ''^~ 

^ 

/'/'/•  '   MoilM 


Jni    /.   /.' 


(  3825  ) 


4300  i  I    +li>^ 


<^  (^Q  ("4000, 
(^:^  (p)  ? 

4075  )  (  4150  ) 

4.501     (^  - 


J'lff  .7  ■Shrr/r 


Fifl  ^>  (T'liit 


^r      -~\  /-\©  ( 

^^H 

^F         5000)  (5050) 

Q^ 

f-    (^    P,©    ' 

1         ^""^    ^--^  /^'"^ 

©     1 

^          /^   ©  € 

)  ^^^    M 

w  ^^1 

^^^^.                    '^~N      [4400 

iifl 

B 

^  ^^^B 

^ 

(6250^       ^^^^-^  ^_^                   ^B 

f    .Q' 

@       ©              @^@l 

1              /■ — s 

@        ^         @                   J 

^ 

^    @      @                      ^ 

^L 

ll 

3  ©  '8^^ 

Mrs  J  Macchdl     i<I 


^ 


12.  Iodine 

in 

Potassium  Iodide. 

odJisb-briiwii 
nniorp.  |)pt. 
'""''  2 -0^1  on  grain. 

•leJdisli-linnvn 
aiiiorp.  ppt. 
.imit  TooWn  g"''"- 

pletldish-brown 
aiiiorji.  ppt. 
'i'"»t  so'oo  grain. 

tleddish-brown 
jj  amorp.  ppt. 
'imit  TSoVncF  grain. 

tteddish-brown  ppt. 
;,imit  :;5oW  grain, 
f'late  viii.,  tigs.  4,  5. 

t  leddisb-brown  ppt. 
jiimit  -^,',s  grain. 
Mate  i.\.,  tig.  Z. 

I 

p)ark-brown  ppt. 
iimit  5 J(jj  grain. 
Mate  ix.,  tig.  5. 

t  leddisb-browD  p)>t. 
,,imit^,\,^^  grain, 
/late  xi.,  tig.  4. 

t#range-bro\vn 
»l  amorp.  ppt. 
a-imit  offr/ooij  grnin. 

lAeddish-brown 
;i  amorp.  ppt. 

psrownish  amorp. 
ppt. 
>™>t  TooW  grain. 


rjleddish-brown 
I  amorp.  ppt. 
'imit  TiJi^ou  grain. 


p^rangc-brown 
amorp.  ]>pt. 
i-irait  -^'^  grain. 

eSrown  amorp.  ppt. 
^timit  ijjjjj  grain. 


13.  Bromine 

in 

Bromohydric  Acid. 

Vollow  amorp.  ppt. 
f-imit  ygJoo  grain. 


Vcllow  amorp.  ppt. 
Limit  ,0000  grain. 


Yellow  amorp.  p|)t. 
Limit  n:^r,  grain. 


Yoliow  amorp.  ppt. 
Limit  TooVoo  gr^'n. 


Yellow  amorp.  ppt. 
Limit  Tjjffn  grain. 


Yellow  amorp.  ppt. 
Limit  yjjJo^  grain. 


Yellow  cryst.  jipt. 
Limit  2^55  grain. 
Plate  ix.,  tig.  0. 

Yellow  amorp.  ppt. 
Limit  r^^oxj-i)  grain. 


Brown  or  3-ellow 

amorp.  ppt. 
Limit  ^lyjgj  grain. 

Yellow  amorp.  ppt. 
Limit  25juij  grain. 


Yellow  cryst.  ppt. 
Limit  ^oJgj  grain. 
Plate  xii.,  Jigs.  5.  0. 


Yellow  amorp.  ppt. 
Limit  TooVon  gniin. 
Plate  xiii.,  fig.  4. 

Bright  yellow  ppt. 


Yellow  or  orange- 
yellow  amorp.  ppt. 
Limit  5^  grain. 

Yellow  amorp.  ppt. 
Limit  55^17  grain. 


SOLUIilLtJY. 


Watkk,  in  III!  proportinn.-!. 
Km  Kit,  freely  soluble. 
Ciii.oRoKORM,  freely  soluble. 

Watkk,  in  100  parts. 
Etiikh,  freely  soluble. 
Ciii.ouoFonM,  freely  soluble. 

Watkr,  in  4160  part.s. 
ErnK.ii,  in  7725  parts. 
Ciii/)ROForcM,  in  6550  part.=. 

Water,  in  25,000  parts. 

Ethkr,  in  209  parts. 

CHr.ouoFOKM,  in  nearly  all  proportions. 

Water,  in  128  parts. 
Ether,  in  54.8  parts. 
Chloroform,  in  21.5  parts. 

Water,  in  1G60  parts. 
Ether,  in  4066  parts. 
CHi.OROFuRJf,  in  7950  part.'. 

Watkr,  in  515  parts. 
Ether,  in  '[?>(S  parts. 
Cnr-OROFORJi,  in  nearly  all  proportions. 

Water,  in  8333  parts.  • 
Ether,  in  1400  parts. 
Chloroform,  in  8  parts. 

Water,  in  900  parts. 
P^THKR,  in  440  parts. 
Chloroform,  very  freely  soluble. 

Water,  in  1783  parts. 

Ether,  in  777  parts. 

Chloroform,  in  nearly  all  proportions. 

Water,  in  414  parts. 
Ether,  freely  soluble. 
CHLOROFOTtM,  in  nearly  all  proportions. 


Water,  in  7860?  parts. 
Ether,  in  108?  ]>arts. 
Chloroform,  freely  soluble. 

Water,  nearly  insoluble. 
Ether,  sparingly  soluble. 
Chloroform,  freely  soluble. 

Water,  in  1750  parts. 
Ether,  in  9000  parts. 
Chloroform,  in  50,000  parts. 

Water  in  644  parts. 
Ether,  freely  soluble. 
CoLOROFORM,  freely  soluble. 


TABULAR    VIKW    OF    THF     BEHAVIOR    OK    CERTAIN     ALKALOIDS    WITH     REAGENTS. 


"  "',     lQ«\?'^*^™in, 


,oJo(  groin.         Llmli  rf,  j 


io5f!"n""r      'pr"to''^"n""2'       i^'-*" 


INDEX. 


Absorpt'ion,  effects  of,  55. 
Acotftte  of  lead,  fatal  quantity,  367. 

General  chemical  nature,  368. 

Period  when  fatal,  366. 

Poisoning  by,  364. 

Post-mortem  appearances,  308. 

Quantitative  analysis,  381. 

Recovery  from  organic  mixtures,  378. 

Solubility,  3G9. 

Special  chemical  properties,  369-378. 

Symptoms  produced  by,  364. 

Treatment  of  poisoning  by,  367. 
Acid,  arsenic,  322. 

Arsenious,  241. 

Comenic,  497. 

Gelsemic,  691. 

Hydrochloric,  poisoning  by,  138- 

Hydrocyanic,  poisoning  by,  168. 

Igasuric,  537. 

Meconic,  495. 

Nitric,  poisoning  by,  119. 

Oxalic,  poisoning  by,  150. 

Phosphoric,  207. 

Pyromeconic,  497. 

Strychnic,  537. 

Sulphuric,  poisoning  by,  98. 
Acids,  mineral,  nature  and  effects  of,  97. 
Aconite,  fatal  quantity,  618. 

Period  when  fatal,  617. 

Poisoning  by,  615. 

Post-mortem  appearances,  623. 

Symptoms  produced  by,  615. 

Treatment  of  poisoning  by,  621. 
Aconitine,  chemical  properties  of,  624. 

Fallacies  of  tests  for,  628. 

History,  613. 

Physiological  test  for,  628. 


Aconitine,  poisoning  by,  615. 
Preparation,  613. 
Recovery  from  the  blood,  630. 
Separation    from   organic   mixtures, 

629. 
Solubility,  625. 
Aconitum  ferox,  613. 

Napellus,  613. 
Ji:sculin,  683. 

.\lkalies,  distinguishing  f)roperties,  61- 
73. 
Fatal  quantity,  65. 
General  chemical  nature  of,  61. 
Pathological  effects  of,  67. 
Period  when  fatal,  64. 
Symptoms  produced  bj',  62. 
Treatment  of  poisoning  by,  66. 
Vegetable,  417. 
Alkaloids,  fixed,  general  nature  of  418. 
Graham  and  Hofmann's  method  for 

recovering,  426. 
Liquid,  417. 
Recovery  by  dialysis.  427. 

By  method  of  Draij;endorff,  429. 
By  method  of  Stas,  418. 
Rodgers  and  Girdwood's  method  for 

recovering,  423. 
Uslar  and  Erdmann's  method  for  re- 
covering, 424. 
.Vmerican  hellebore,  657. 
.\mmonia,  carbonate  of,  64. 
Density  of  solutions  of,  89. 
Effects  of  vapor,  64. 
Fatal  quantity,  65. 
General  chemical  nature,  89. 
Period  when  fatal,  64. 
Quantitative  analysis,  96. 

775 


776 


AMM — ATR 


Ammonia,    separation    from     organic 
mixtures,  95. 

Special  chemical  properties,  90-95. 

Symptoms  produced  by,  63. 
Analyses,    precautions    in    regard    to, 

48. 
Analysis,  substances  requiring,  47. 
Analyst,  qualifications  requisite,  58. 
Aniline,  source  of  fallacy,  570. 
Antimonuretted  hydrogen,  227. 
Antimony,  history  of,  217. 

Quantitative  analysis,  238. 

Eecovery  from  the  tissues,  236. 

Eecovery  from  the  urine,  237. 

Separation  from  complex  mixtures, 
233. 
Apparatus,  chemical,  58. 
Appeamnces,  post-mortem,  44. 
Aqua    ammonise,    chemical   properties 
of,  89. 

Poisoning  by,  63. 
Aqua  fortis,  119. 
Arsenic,  compounds  of,  241. 

Eating  of,  36. 

Metallic,  history,  239. 
Physiological  effects,  240. 
Special  chemical  properties,  240. 

White,  241. 
Arsenic  acid,  ammonio-copper  sulphate 
test,  325. 

Physiological  effects  of,  322. 

Quantitative  analysis,  328. 

Eeinsch's  test  for,  326. 

Special  chemical  properties,  323. 

Sulphuretted  hydrogen  test,  323. 
Arsenic  oxide  and  acid,  general  chem- 
ical nature,  322. 
Arsenious  acid,  241. 
Arsenious  oxide,  241. 

Antidotes  for,  247. 

Antiseptic  properties  of,  251. 

Bettendorff's  test,  295. 

Danger  and  Piandin's  method,  307. 

Detection  after  long  periods,  312. 
In  the  stomach,  299. 
In  vomited  matters,  298. 

Distribution  of  absorbed,  310. 

Duflos  and  Hirsch's  method,  308. 


Arsenious  oxide,   external  application 

of,  245. 
Failure  to  detect,  312. 
Fallacies  of  Eeinsch's  test,  275. 

Of  sulphur  test,  269. 
Fatal  quantity,  246. 
Fresenius  and  Babo's  method,  301. 
General  chemical  nature,  252. 
Iodide  of  potassium  test,  296. 
Lime-water  test,  296. 
Marsh's  test,  279. 

Bloxam's  modification,  293. 

Delicacy  of,  283,  287,  291. 

Fallacies  of,  285,  288,  291. 
Nitrate  of  silver  test,  261. 
Period  when  fatal,  246. 
Post-mortem  appearances,  250. 

Diffusion,  313. 
Quantitative  analysis,  321. 
Recovery  from  the  urine,  P>09. 
Reduction  test,  257. 
Reinsch's  test,  271. 

Interferences  of,  278. 
Separation    from   organic   mixtures, 
297. 

From  the  tissues,  300. 

Gautier's  method,  306. 
Solubility  in  alcohol,  256. 

In  chloroform,  256. 

In  water,  2-53. 
Solutions  of,  260. 
Sublimation  test  for,  256. 
Sulphate  of  copper  test,  263. 
Sulphuretted  hydrogen  test,  264. 
Symptoms  produced  by,  242. 
Taste  of,  242. 
Time  of  symptoms,  244. 
Treatment  for,  247. 
Vaporization  of,  252. 
Varieties  of,  242. 
Asagrsea  officinalis,  653. 
Atropa  belladonna,  631. 
Atropia,  631. 

Atropine,  chemical  properties  of,  640. 
External  application  of,  638. 
History,  631. 
Physiological  test,  645. 
Poisoning  by,  633. 


ATR — COM 


777 


Atropine,     post-mortem     appeiiriinces, 

(•.39. 
Preparation,  031. 
Recovery  from  the  blood,  047. 
Separation   from  complex  inixture.«. 

645. 
Solubility,  640. 

Subcutaneous  injection  of,  037. 
Treatment  for  poisoning  by,  038. 

Belladonna,  poisoning  by,  033. 
Post-mortem  appearances,  039. 
Symptoms  produced  bj",  633. 
Treatment  of  poisoning  by,  038. 
Bettendorff's  test  for  arsenic,  295. 
Biiioxalate  of  potassium,  poisoning  bv, 

72. 
Bismuth  nitrate,  310. 
Bittersweet,  673. 
Blood,  physical  characters,  701. 
Composition  of,  701. 
Eed  corpuscles,  702. 

Action  of  water  on,  705. 
"White  corpuscles,  706. 
Blood-stains,  707. 
Chemical  tests  for,  708. 
Heat,  708. 
Ammonia,  709. 
Guaiacum  test,  709. 
Hfemin  crystals,  711. 
Optical  properties,  714. 
Micro-spectroscope,  714. 
Blood-spectra,  715. 
Examination  of  stains,  718. 
Fallacies,  720. 
Microscopic  detection  and  discrimi- 
nation, 721. 
Oviparous  blood,  721. 
Mammalian  blood,  723. 
Limit  of  determining  differences, 

723. 
Measurement  by  the   microscope, 

725. 
Average  size  of  mammalian  cor- 
puscles, 728. 
Table  of,  733. 

Limit  of  discrimination,  735. 
Examination  of  dried  blood,  737. 


Blood,  liquids  employed  for  examina- 
tion of,  737. 
Fallacies,  739. 
Location  of  .^tains,  740. 
Blood-sucking  insects,  741. 
Bloxara's  method  for  detecting  arsenic, 

293. 
Blue  vitriol,  883. 
Brucia,  600. 

Brucine,  general  chemical  nature,  600. 
History,  000. 

Xitric  acid  and  tin  test,  003. 
Physiological  effects,  601. 
Preparation,  600. 
Recovery  from  the  blood,  612. 

From  the  stomach,  611. 
Separation   from   organic   mixtures, 

611. 
Solubility,  601. 

Special  chemical  properties,  002. 
Sulphuric  acid  and  nitre  test,  005. 
Test  for  nitric  acid,  129. 
Buffenbarger,  Peter,  case,  252. 
Burnett's  disinfecting  fluid,  402. 

CESIUM,  01. 

Carbonic  oxide  haemoglobin,  717. 
Causes  modifying  effects  of  poisons,  3-5. 
Cerebral  poisons,  37. 
Cevadine,  654. 

Chemical  analysis,  importance  of,  49. 
Failure  of,  54, 

Decomposition  of  poisons,  56. 

Reagents,  50. 

Tests,  value  of,  50. 
Chemicals,  arsenic  in,  316. 
Chloride  of  zinc,  poisoning  by,  403. 
Classification  of  poisons,  37. 
Codeia,  523. 
Codeine,  general  chemical  nature,  524. 

History,  523. 

Preparation,  523. 

Physiological  effects,  523. 

Salts  of,  524. 

Solubility,  525. 

Tests  for,  52-5-528. 
Comenic  acid,  497. 
Compound  poisoning,  39. 


778 


CON — GEL 


Conia,  453. 
Conicine,  453. 

Conine,    distinguished    from    nicutine, 
463. 

Fallacies  of  tests  for,  463. 

General  chemical  nature,  456. 

History,  453. 

Physiological  effects  of,  454. 

Preparation,  453. 

Solubility,  457. 

Special  chemical  properties,  457-463. 

Eecovery  from  the  blood,  464. 

Salts  of,  459. 

Separation   from    organic    mixtures, 
464. 
Conium  maculatum,  453. 
Copper,  chemical  properties  of  salts  of, 
387. 

Combinations,  383. 

Fatal  quantity,  385. 

History  and  chemical  nature,  382. 

Period  when  fatal,  385. 

Physiological  effects,  383. 

Post-mortem  appearances,  386. 

Quantitative  analysis,  400. 

Eecovery  from  organic  mixtures,  396. 
From  the  tissues,  398. 
From  the  urine,  399. 

Solutions  of,  387. 

Special  chemical  properties,  387. 

Subacetate,  383. 

Sulphate,  383. 

Symptoms  produced  by,  384. 

Treatment  of  poisoning  by,  386. 
Corrosive  sublimate,  chemical  proper- 
ties, 340. 

Ammonia  test  for,  343. 

Chloride  of  tin  test,  347. 

Chronic  poisoning  by,  334. 

Composition,  331. 

Copper  test  for,  348. 

External  application,  334. 

Failure  to  detect,  361. 

Fatal  quantity,  335.        ' 

General  chemical  nature,  339. 

Period  when  fatal,  335. 

Poisoning  by,  331. 

Post-mortem  appearances,  337. 


Corrosive  sublimate,  quantitative  anal- 
ysis, 362. 

Eecovery  from  organic  mixtures,  354. 
From  the  urine,  360. 

Eeduction  test,  342. 

Solubility,  339. 

Sulphuretted  hydrogen  test,  345. 

Symptoms  produced  by,  331. 

Treatment  of  poisoning  by,  336. 
Curara,  properties  of,  571. 
Curarine,  570. 

Danger  and  Flandin's  method  for  de- 
tecting arsenic,  307. 

Datura  stramonium,  647. 

Daturia,  647. 

Daturine,  chemical  properties,  651. 
History,  647. 
Preparation,  648. 
Recovery  from  the  blood,  652. 
Separation   from   organic    mixtures, 
652. 

Davy's  method  for  arsenic,  295. 

Dialysis,  method  of  application,  427. 

Disease,  modifying  influence  of,  36. 

Diseases  simulating  poisoning,  40. 

Duflos   and    Hirsch's    method   for   de- 
tecting arsenic,  308. 

Elimination  of  poisons,  55. 
Evidences  of  poisoning,  38. 

From  chemical  analysis,  47. 

From  post-mortem  appearances,  43. 

Prom  symptoms,  38. 

Fabrics,  arsenic  in,  318. 
Failure  to  detect  a  poison,  54. 
Fleitmann's  test  for  arsenic,  294. 
Freet,  case,  549. 

Fresenius  and  Babo's  method  of  analy- 
sis, 301. 

Galvanized  iron,  poisoning  by,  404. 
Gelsemia,  683. 
Gelsemic  acid,  683. 

Chemical  properties,  691. 

Preparation,  684. 

Reactions  with  reagents,  693. 


(JKI, —  LKA 


779 


Gelsemic  acid,  recovery  from  ori^iinic 
mixtures,  698. 
From  the  blood,  700. 
From  the  ti.ssues,  700. 
Solubility,  692. 
(iclscmine,  683. 

Chemical  properties,  694. 
In  solid  state,  095. 
In  solution,  096. 
Fatal  quantity,  688. 
Pathological  effects,  690. 
Period  when  fatal,  687. 
Recovery     from    organic     mixtures, 
698. 
From  the  blood,  700. 
From  the  tissues,  699. 
wSolubility,  095. 
Symptoms  produced  by,  G85. 
Treatment,  689. 
Gelsemium  sempervirens,  683. 

Preparations  of,  685. 
Glass,  arsenic  in,  319. 
Graham    and    Hofmann's    method    for 
recovering  strychnine,  426. 

Habit,  modifying  influence  of,  35. 
Hajmatin,  717. 
Haemoglobin,  716. 

Hellebore,    American,    poisoning    by, 
6.57. 

White,  poisoning  by,  656. 

Post-mortem  appearances,  660. 

Symptoms,  657. 

Treatment,  660. 
Hemlock,   detection   in    oi-ganic    mix- 
tures, 464. 

Poisoning  by,  4-54. 

Post-mortem  appearances,  456. 

Symptoms  produced  by,  454. 

Treatment  of  poisoning  by,  455. 
Hydrochloric  acid,  density  of  solutions 
of,  142. 

Fatal  quantity,  140. 

General  chemical  nature,  141. 

Period  when  fatal,  139. 

Poisoning  by,  138. 

Post-mortem  appearances,  141. 

Quantitative  analysis,  148. 


Hydrochloric   acid,   rccoverj'  from    or- 
ganic mixtures,  146. 

Recovery  from  organic  fabrics,  148. 

Special  chemical  properties,  143-146. 

Symptoms  produced  by,  138. 

Test  for  meconic  acid,  497. 

Treatment  of  poisoning  by,  141. 
Hydrocyanic   acid,    failure    to    detect, 
192. 

Fatal  quantity,  173. 

General  chemical  nature,  177. 

History  and  composition,  167. 

Period  when  fatal,  172. 

Poisoning  by,  168. 

Post-mortem  appearances,  175. 

Quantitative  analysis,  192. 

Recovery  from  the  blood,  191. 

Separation    from    organic   mixtures, 
187. 

Special  chemical  properties,  178-187. 

Symptoms  produced  by,  168. 

Treatment  of  poisoning  by,  174. 
Hydrofluosilicic  acid  as  a  reagent,  81. 
Hyoscine,  6-52. 

Idiosyncrasy,  effects  of,  35. 

Igasuric  acid,  537. 

Indian  poke,  657. 

Intestines,  perforation  of,  46. 

Irritant  poisoning,  morbid  appearances 

in,  45. 
Irritant  poisons,  effects  of,  37. 

Jamestown  weed,  poisoning  by,  647. 

Japaconitine,  613. 

Jervine,  chemical  properties,  667. 

History,  653. 

Preparation,  655. 

Separation   from    organic   mixtures, 
670. 
From  the  blood,  671. 

Solubility,  667. 
Jessamine,  683. 

Lamson^  case,  621. 
Laudanum,  467. 

Lead    acetate,    chronic    poisoning   by, 
365. 


780 


LEA XIC 


Lead  acetate,  fatal  quantity,  367. 
General  chemical  nature,  368. 
Period  when  fatal,  366. 
Post-mortem  appearances,  368. 
Solubility,  369. 

Special  chemical  properties,  369. 
Symptoms  produced  by,  364. 
Treatment  of  poisoning  by,  367. 
Detection  in  the  urine,  381. 
External  application  of,  366. 
History  and  chemical  nature,  363. 
Physiological  effects  of,  364. 
Quantitative  analysis,  381. 
Separation   from   organic   mixtures, 
378. 
Prom  the  tissues,  380. 
Sulphuretted  hydrogen  test  for,  371. 
Lithium,  chemical  properties  of,  61. 
Lloyd,  iSIrs.  E.,  case,  317. 

Mallet.  Prof.,  aconite  poisoning,  618. 
Marsh's  test  for  arsenic,  279. 
Meconie  acid,  failure  to  detect,  513. 

General  chemical  nature,  496. 

History,  495. 

Iron  test  for,  497. 

Physiological  effects  of,  496. 

Preparation,  495. 

Pecovery  from  the  blood,  511. 
From  the  tissues,  510. 

Separation   from   organic   mixtures, 
503. 

Solubility,  496. 

Special  chemical  properties,  497-503. 
Meconine,  533. 
Medicines,  arsenic  in,  316. 
Mercury,  compounds  of,  330. 

Detection  in  the  urine,  360. 

Metallic,  properties  of,  330. 

Physiological  effects,  330. 
Methsemoglobin,  716. 
Meyer,  Dr.,  case,  620. 
Micro-chemistry  of  poisons,  definition. 

33, 
Microscope,  application  of,  34. 
Mineral  acids,  nature  and  effects  of,  97. 
Monkshood,  613.  , 
Morphia,  476. 


Morphine,  external  application  of,  479. 
Pailure  to  detect,  513. 
Patal  quantity,  477. 
General  chemical  nature,  480. 
History  and  preparation,  476. 
Nitric  acid  test  for,  485. 
Period  when  fatal,  477. 
Post-mortem  appearances,  480. 
Quantitative  analysis,  514. 
Kecovery  from  the  blood,  511. 

Prom  organic  mixtures,  503. 

Prom  the  tissues,  510. 

Prom  the  urine,  513. 
Separation    from    organic   mixtures, 

503. 
Solubility,  480. 

Special  chemical  properties,  483-495. 
Symptoms  produced  by,  476. 
Treatment  of  poisoning  by,  480. 
Muriatic  acid,  138. 

Xarceine,  chemical  tests  for,  529-532. 

General  chemical  nature,  529. 

History,  529. 

Physiological  effects,  529. 

Preparation,  -529. 

Solubility,  530. 
Narcotic  poisoning,  morbid  effects  of, 

44. 
Narcotic  poisons,  symptoms  of,  37. 
Narcotico-irritant  poisoning,  37. 
Narcotine,    general    chemical    nature, 
516. 

History,  515. 

Physiological  effects  of,  515. 

Preparation,  515. 

Solubility,  516. 

Special  chemical  properties,  517-522. 

Test  for  nitric  acid,  131. 
Nessler's  test  for  ammonia,  93. 
Nicotia,  434. 
Nicotiana  tabacum,  434. 
Nicotine,  general  chemical  nature,  439. 

Hi-story,  434. 

Period  when  fatal,  437. 

Post-mortem  appearances,  438. 

Preparation,  434. 

Kecovery  from  the  blood,  4.50. 


Nrc — pi< 


781 


Nicotine,  recovery  from  orgunif  mix- 
tures, 447. 
From  the  tissues,  450. 

Suits  of,  441. 

Solubility,  439. 

Special  chemical  properties,  440-447. 

Symptoms  produced  by,  43o. 

Treatment  of  poisoning  by,  438. 
Nightshade,  deadly,  G31. 

Garden,  symptoms  of.  072. 

Woody,  672. 
Nitrate  of  potassium,  poisoning  by,  69. 
Nitric  acid,  anhydrous,  123. 

Antidotes  for,  121. 

Density  of  solutions  of,  124. 

Fatal  quantity,  121. 

Fumes  of,  fatal,  120. 

General  chemical  nature,  123. 

Pathological  effects,  121. 

Period  when  fatal,  121. 

Poisoning  by,  119. 

Quantitative  analysis,  137. 

Recovery  from  organic  fabrics,  136. 
From  organic  mixtures,  134. 

Special  chemical  properties,  124-133. 

Symptoms  produced  by,  119. 
Nux  vomica,  chemical  propertie.',  541. 

Fatal  quantity,  539. 

History  and  composition.  537. 

Period  when  fatal,  539. 

Physical  properties,  541. 

Post-mortem  appearances,  .540. 

Symptoms  produced  by,  537. 

Treatment  of  poisoning  by,  540. 

(Esophagus,  perforation  of,  46. 
Oil  of  vitriol,  poisoning  by,  98. 
Opianyl,  chemical  tests  for,  533-536. 

General  chemical  nature,  533. 

History,  533. 

Physiological  effects  of,  533. 

Preparation,  533. 

Solubility,  534. 
Opium,  effects  of  enema  of,  469. 

Effects  of  external  application,  469. 

Failure  to  detect,  513. 

Fatal  quantity,  470. 

History  and  chemical  nature,  466. 


Opium,  period  when  fatal,  469. 

Physical    and   chemical    properties, 
475. 

Post-mortem  appearance?,  474. 

Recovery  after  large  doses  of,  471. 
From  organic  mixtures,  503. 

Symptoms  produced  by,  467. 

Time  of  symptoms,  468. 

Treatment  of  poisoning  by,  472. 
Orpiment,  241,  264. 
Oxalic  acid,  fatal  quantity,  153. 

General  chemical  nature,  155. 

History,  1.50. 

Period  when  fatal,  152. 

Poisoning  by,  150. 

Post-mortem  appearances,  1-54. 

Quantitative  analysis,  166. 

Eecovery  from  organic  mixtures,  162. 
From  the  urine,  166. 

Solubility,  1.56. 

Special  chemical  properties,  156-162. 

Symptoms  produced  by,  150. 

Treatment  of  poisoning  by,  154. 
Oxy-hsemoglobin,  715. 

Papater  somniferum,  466. 
Phosphoric  acid,  general  chemical  na- 
ture, 207. 

Special  chemical  properties,  208-212. 
Phosphorus,  failure  to  detect,  215. 

Fatal  quantity,  196. 

General  chemical  nature,  199. 

History,  193. 

Hydrogen  test,  205. 

Lipowitzs  test,  207,  214. 

Mitscherlich^s  test,  202,  213. 

Period  when  fatal,  195. 

Poisoning  by,  193. 

Post-mortem  appearances,  198. 

Quantitative  analysis,  216. 

Recovery  as  oxide,  215. 

From  organic  mixtures,  212. 

Solubility,  200. 

Special  chemical  properties,  201-207. 

Symptoms  produced  by,  193. 

Treatment  of  poisoning  by,  197. 

Varieties  of,  200. 
Picraconitine,  613. 


782 


PIL — STR 


Pilocarpine,  639. 
Poison,  definition  of,  34. 

Failure  to  detect,  54. 
Poisons,  classification  of,  37. 
Polarized  ligbt,  tests  for  sodium,  87. 
Porphyroxin,  509. 

Post-mortem  appearances,  as  evidence 
of  poisoning,  44. 

Diffusion,  313. 

Examinations,  46. 
Potassium  chlorate,  70. 
Nitrate,  69. 
Oxalate,  72. 
Tartrate,  72. 

Density  of  solutions  of,  74. 

Patal  quantity,  65. 

General  chemical  nature,  73. 

Period  when  fatal,  64. 

Picric  acid  test  for,  80. 

Platinum  test  for,  76. 

Post-mortem  appearances,  67. 

Quantitative  analysis,  84. 

Kecovery  from  organic  mixtures,  83. 

Special  chemical  properties,  73-75. 

Sulphate,  poisoning  by,  72. 

Symptoms  produced  by,  62. 

Tartaric  acid  test  for,  78. 

Tartrate,  poisoning  by,  72. 

Treatment  of  poisoning  by,  66. 
Prussic  acid,  167. 
Pseudaconitine,  613. 
Ptomaines,  431. 
Pyromeconic  acid,  497. 

EATSBAJfE,  241. 

Eeagents,  chemical,  56. 

Kealgar,  241. 

Reinsch's  test  for  arsenic,  271. 

Eodgers   and   Girdwood's   method  for 

recovering  alkaloids,  423. 
Eubidium,  61. 

Sababilla,  653. 

Sodium  hydrate,  density  of  solutions  of, 
85. 

General  chemical  nature,  84. 

Poisoning  by,  62. 

Recovery  from  organic  mixtures,  89. 


Sodium  hydrate,  special  chemical  prop- 
erties, 85-88. 
Solania,  672. 
Solanine,  chemical  properties  of,  675. 

History,  672. 

Preparation,  672. 

Post-mortem  appearances,  675. 

Recovery  from  organic  mixtures,  681. 

Solubility,  676. 

Symptoms  produced  by,  674. 

Treatment  of  poisoning  by,  675. 
Solanum     dulcamara,     symptoms     of, 
673. 

Nigrum,  symptoms  of,  673. 

Tuberosum,  poisoning  by,  674. 
Sonnenschein's  test  for  ammonia,  95. 
Sources  of  evidence  of  poisoning,  38. 
Spectrum  analysis,  82. 
Spinal  poisons,  38. 
Spirit  of  salt,  138. 
Stas's  method  for  recovering  alkaloids, 

418. 
Stramonium,  external  application,  650. 

Poisoning  by,  648. 

Post-mortem  appearances,  651. 

Symptoms  produced  by,  648. 

Treatment  for  poisoning  by,  650. 
St.  Ignatius'  bean,  542. 
Stomach,  redness  of,  44. 

Softening  of,  45. 

Ulceration  and  perforation,  45. 
Strychnia,  542. 
Strychnic  acid,  537. 
Strychnine,    accumulative    eft'ects    of, 
548. 

Color  test  for,  562. 
Delicacy  of,  564. 
Fallacies  of,  569. 
Interferences  with,  566. 

External  application  of,  547. 

Failure  to  detect,  597. 

Fatal  quantity,  550. 

Frog  test  for,  584. 

Galvanic  test,  574. 

General  chemical  nature,  557. 

History,  542. 

Period  when  fatal,  549. 

Physiological  test  for,  584. 


RTR — VOM 


783 


Strychniiio     j)uisoniiii^,    diagnosis    of, 
548. 
Post-iiii>rtom  appearances,  565. 
Preparation,  542. 
Quantitative  analysis,  GOO. 
Recovery  from  the  blood,  598. 
From  mix  vomica,  586. 
From  orijanie  mi.\tures,  587. 
From  the  tis.^ucs,  500. 
From  the  urine,  59(i. 
By  dialysis,  590. 
Salts  of,  559. 
Solubility,  558. 

Special  chemical  properties,  559. 
Symptoms  produced  by,  543. 
Taste  of,  559. 
Time  of  symptoms,  540. 
Treatment  of  poisoning  by,  552. 
Strychnos  Ignatii,  542. 
Sugar  of  lead,  poisoning  by,  364. 
Sulphate  of  potassium,  72. 
Sulphuric  acid,  density  of  solutions  of, 
106. 
Fatal  quantity,  101. 
General  chemical  nature,  105. 
Period  when  fatal,  100. 
Poisoning  by,  98. 
Post-mortem  appearances,  102. 
Quantitative  analysis,  118. 
Recovery    from     organic    mixtures, 

113. 
Separation  from  organic  fabrics,  118. 
Special  chemical  properties,  106-112. 
Symptoms  produced  by,  98. 
Treatment  of  poisoning  by,  101. 
Suspected  poisoning,  42. 
Symptoms,   as  evidence  of  poisoninsj. 
38. 

Tartar  emetic,  composition,  217. 
Fatal  quantity,  220. 
General  chemical  nature,  222. 
Period  when  fatal,  219. 
Post-mortem  appearances,  221. 
Quantitative  analysis,  238. 
Recovery  from  organic  mixtures,  233. 

From  the  tissues,  236. 

From  the  urine,  237. 


Tartar  cniotic,  .solubility,  222, 

Special  chemical  j)roportic8,  223. 

.Symptoms  produced  by,  218. 

Treatment,  221. 
Tartrate  of  potassium,    poisoning   by, 

72. 
Tetanus,  distinguished  from  poisoning, 

548. 
Thorn-apple,  647. 

Tincture  of  opium,  [)oisoning  by,  467. 
Tobacco,  chemical  prcjporties  of,  439. 

Detection  in  organic  mixture.«.  447. 

External  application  of,  43G. 

Fatal  quantity,  438. 

Period  when  fatal,  437. 

Poisoning  by,  435. 

Post-mortem  appearances,  438. 

Smoking  of,  436. 

Symptoms  produced  by,  435. 

Treatment  of  poisoning  by,  438. 

UsLAR  and  Erdmann's  method  for  re- 
covering alkaloids,  424. 

Valser's  method  for  recovery  of  mor- 
phine, 508. 
Vegetable  alkaloids,  417. 

Poisons,  general  considerations,  417. 
Veratralbine,  654. 
Veratria,  653. 
Veratrine,  chemical  properties,  660. 

History,  653. 

Poisoning  by,  656. 

Preparation,  654. 

Recovery  from  organic  mixtures,  670. 
From  the  blood,  671. 

Salts  of,  661. 

Solubility,  662. 

Test  for  sulphuric  acid,  112. 
Veratroidia,  653. 
Veratrum  album,  653. 

Post-mortem  appearances,  660. 

Sabadilla,  653. 

Treatment,  660. 

Viride,  poisoning  by,  657. 
Verdigris,  383 
Viridia,  653. 
Vomiting,  effects  of,  54. 


784 


WAL— ZIN 


Wall- Papers,  arsenic  in,  318. 

White  hellebore,  poisoning  by,  656. 

White  vitriol,  402. 

Wolfsbane,  613. 

Woorara,  properties  of,  571. 

Yellow  jessamine,  683. 

Zinc,  chloride  of,  402. 

History  and  chemical  nature,  400. 
Post-mortem  appearances,  405. 


Zinc,  properties  of  salts  of,  402. 
Quantitative  analysis,  413. 
Kecovery    from    organic    mixtures, 

412. 
Salts  of,  402. 
Solutions  of,  407. 
Special  chemical  properties,  406. 
Sulphate  of,  402. 
Symptoms  produced  by,  402. 
Treatment  of  poisoning  by,  405. 
Use  of,  for  culinary  purposes,  404. 


THE    END. 


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